[Correction with related applications]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0019892 dated February 20, 2019, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
[Technical field]
[4]
The present invention relates to an olefin-based polymer, and more particularly, to a low-density olefin-based polymer having multiple crystallinity and exhibiting a low flow index prepared by using two types of transition metal compound catalysts.
background
[5]
Polyolefin has excellent moldability, heat resistance, mechanical properties, sanitary quality, water vapor permeability and appearance characteristics of molded products, and is widely used for extrusion molded products, blow molded products and injection molded products. However, polyolefins, particularly polyethylene, have low compatibility with polar resins such as nylon and low adhesion to polar resins and metals because they do not have polar groups in their molecules. As a result, it has been difficult to blend polyolefins with polar resins or metals or laminate them with these materials. In addition, polyolefin molded articles have problems with low surface hydrophilicity and antistatic properties.
[6]
In order to solve such a problem and increase affinity for a polar material, a method of grafting a polar group-containing monomer onto a polyolefin through radical polymerization has been widely used. However, in this method, intramolecular crosslinking of polyolefin and cleavage of molecular chains occurred during the graft reaction, so that the viscosity balance between the graft polymer and the polar resin was poor, and miscibility was low. In addition, there was a problem in that the appearance characteristics of the molded article were low due to the gel component generated by intramolecular crosslinking or foreign substances generated by the cleavage of molecular chains.
[7]
In addition, as a method for producing an olefin polymer such as an ethylene homopolymer, an ethylene/α-olefin copolymer, a propylene homopolymer or a propylene/α-olefin copolymer, a polar monomer is copolymerized under a metal catalyst such as a titanium catalyst or a vanadium catalyst. method was used. However, when the polar monomer is copolymerized using the metal catalyst as described above, there is a problem in that the molecular weight distribution or composition distribution is wide and the polymerization activity is low.
[8]
As another method, a method of polymerization in the presence of a metallocene catalyst composed of a transition metal compound such as zircononocene dichloride and an organoaluminum oxy compound (aluminoxane) is known. When a metallocene catalyst is used, a high molecular weight olefin polymer is obtained with high activity, and the resulting olefin polymer has a narrow molecular weight distribution and a narrow composition distribution.
[9]
In addition, a non-crosslinked cyclopentadienyl group, a crosslinked or uncrosslinked bisindenyl group, or a metallocene compound having a ligand of an ethylene bridged unsubstituted indenyl group/fluorenyl group is used as a catalyst to produce a polyolefin containing a polar group. As the method, a method using a metallocene catalyst is also known. However, these methods have the disadvantage of very low polymerization activity. For this reason, although a method of protecting a polar group with a protecting group has been implemented, when the protecting group is introduced, the protecting group must be removed again after the reaction, thereby complicating the process.
[10]
The ansa-metallocene compound is an organometallic compound including two ligands connected to each other by a bridge group, and rotation of the ligand is prevented by the bridge group, and the activity of the metal center and structure is determined.
[11]
Such an ansa-metallocene compound is used as a catalyst in the preparation of an olefin-based homopolymer or copolymer. In particular, it is known that an ansa-metallocene compound containing a cyclopentadienyl-fluorenyl ligand can produce high molecular weight polyethylene, thereby controlling the microstructure of polypropylene. have.
[12]
In addition, it is known that the ansa-metallocene compound containing an indenyl ligand has excellent activity and can prepare polyolefins with improved stereoregularity.
[13]
As such, various studies have been made on ansa-metallocene compounds capable of controlling the microstructure of olefinic polymers while having higher activity, but the degree is still insufficient.
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[14]
An object of the present invention is to provide a low-density olefin-based polymer having multiple crystallinity, low flow index, and improved mechanical properties, prepared using two types of transition metal compound catalysts.
means of solving the problem
[15]
In order to solve the above problems, the present invention (1) cross-fractionation chromatography (CFC, Cross-fractionation Chromatography) in the temperature range of -20 ℃ to 120 ℃ -20 ℃ soluble fraction (SF, Soluble Fraction) has two peaks except, T(90)-T(50)<8.0°C (T(90) is the temperature at which 90% by weight of the olefinic polymer is eluted, and T(50) is 50% by weight of the olefinic polymer is the elution temperature); (2) the soluble fraction (SF, Soluble Fraction) at -20 ℃ on cross-fractionation chromatography (CFC, Cross-fractionation Chromatography) 10% by weight or less; (3) 15°C < Te (elution temperature) < 50°C; and (4) Te (elution temperature) has a linear correlation with the density of the polymer, satisfies Equation 1 below, and provides a multi-crystalline olefinic polymer.
[16]
[Equation 1]
[17]
Te = 1,220×Density-A
[18]
(1,031≤A≤1,039)
Effects of the Invention
[19]
The olefin-based polymer according to the present invention is a low-density olefin-based polymer and exhibits excellent mechanical properties, such as improved tensile strength, tear strength, and flexural modulus, by relatively increasing the ratio of high crystalline regions.
Brief description of the drawing
[20]
1 is a graph showing the CFC dissolution curve of Example 1 and Comparative Example 1.
[21]
2 is a graph showing the correlation between the density of the polymers of Examples 1 to 5 and Comparative Examples 1 to 4 and Te (elution temperature).
[22]
3 is a graph showing the GPC molecular weight distribution curves of Example 1 and Comparative Example 1.
Best mode for carrying out the invention
[23]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[24]
The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[25]
As used herein, the term "polymer" refers to a polymer compound prepared by polymerization of monomers of the same or different types. The generic term "polymer" includes the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer". Also, the term “interpolymer” refers to a polymer prepared by polymerization of two or more different types of monomers. The generic term "interpolymer" refers to the term "copolymer" (which is commonly used to refer to polymers prepared from two different monomers), as well as the term "copolymer" (usually used to refer to polymers prepared from three different types of monomers). used) the term "terpolymer". This includes polymers prepared by polymerization of four or more types of monomers.
[26]
[27]
The olefin-based polymer according to the present invention is polycrystalline and satisfies the requirements of (1) to (4) below.
[28]
(1) Cross-fractionation chromatography (CFC) has two peaks except for the soluble fraction (SF, Soluble Fraction) at -20 ° C in the temperature range of -20 ° C to 120 ° C when measured, and T (90 )-T(50)<8.0°C (T(90) is the temperature at which 90% by weight of the olefinic polymer is eluted, and T(50) is the temperature at which 50% by weight of the olefinic polymer is eluted);
[29]
(2) the soluble fraction (SF, Soluble Fraction) at -20 ℃ on cross-fractionation chromatography (CFC, Cross-fractionation Chromatography) 10% by weight or less;
[30]
(3) 15°C < Te (elution temperature) < 50°C; and
[31]
(4) Te (elution temperature) has a linear correlation with the density of the polymer, and satisfies Equation 1 below
[32]
[Equation 1]
[33]
Te = 1,220×Density-A
[34]
(1,031≤A≤1,039)
[35]
[36]
(1) has two peaks except for the soluble fraction (SF, Soluble Fraction) at -20 °C in the temperature range of -20 °C to 120 °C when measured by cross-fraction chromatography (CFC), T(90)-T(50) )<8.0℃
[37]
Here, T(90) is the temperature at which 90% by weight of the olefin-based polymer is eluted, and T(50) is the temperature at which 50% by weight of the olefin-based polymer is eluted.
[38]
[39]
The olefin-based polymer of the present invention has two peaks except for the soluble fraction (SF, Soluble Fraction) at -20 ° C in the temperature range of -20 ° C to 120 ° C when measured by Cross-fractionation Chromatography (CFC). , the difference between the elution temperature T(50) when the elution amount of the olefinic polymer is 50% by weight and the elution temperature T(90) when the elution amount is 90% by weight, T(90)-T(50) is less than 8°C is satisfied with The T(90)-T(50) may be specifically 7.8 °C or less, more specifically 1 °C to 7.8 °C, and even more specifically 5 °C to 7.8 °C.
[40]
The measurement of the CFC used herein may be measured using, for example, a CFC machine manufactured by PolymerChar, and may be measured while raising the temperature from -20°C to 120°C using o-dichlorobenzene as a solvent.
[41]
In general, when two or more olefin-based polymers having different densities and crystallinity are prepared in separate reactors and then blended, two peaks may appear in the TREF and CFC measurements of this composition or the olefin block copolymer. However, in the present invention, unlike this, by controlling the crystallinity distribution through continuous solution polymerization in a single reactor, two peaks are shown when TREF or CFC is measured without forming a block in the polymer, and T(90)-T( 50) satisfies the above value, so the difference is small.
[42]
The olefin-based polymer according to an example of the present invention may have a T (90) of 20° C. or higher when measured TREF or CFC, specifically 20° C. to 60° C., and more specifically 25° C. to 40° C. In addition, the olefin-based polymer according to an example of the present invention may have a T (50) of less than 40° C. when measured TREF, specifically 35° C. or less, and more specifically, 15° C. to 35° C.
[43]
In addition, in the present invention, T(50) is the temperature at the time when 50% by weight of the total elution amount in the TREF or CFC elution curve expressed as the elution amount with respect to temperature (dC/dT) means the temperature at which the dissolution ends, and T(90) ) means the temperature at which 90% by weight of the total dissolution is terminated in the CFC dissolution curve expressed as the dissolution amount (dC/dT) with respect to temperature, and T(90)-T(50) is T(90) and T(50) represents the difference between the two temperatures.
[44]
[45]
(2) The soluble fraction (SF, Soluble Fraction) at -20 ℃ on cross-fractionation chromatography (CFC, Cross-fractionation Chromatography) is 10% by weight or less
[46]
In addition, in the olefin-based polymer of the present invention, the soluble fraction (SF, Soluble Fraction) at -20 ° C on cross-fractionation chromatography (CFC) is 10 wt% or less, specifically 0.2 wt% to 5 wt% % by weight, and more specifically 0.2% to 4% by weight.
[47]
In the cross-fractionation chromatography (CFC, Cross-fractionation Chromatography) measurement, the fraction eluted at a lower temperature has lower crystallinity, and in the present specification, the cross-fractionation chromatography (CFC) at -20°C or lower The eluted soluble fraction (SF, Soluble Fraction) is defined as an ultra-low crystallinity region.
[48]
In general, the lower the density of the polymer, the lower the crystallinity, the increase in the ultra-low crystallinity region, and the impact strength is improved. However, when the ultra-low crystallinity region exceeds a certain level in a typical olefin-based polymer, mechanical properties deteriorate. The olefin-based polymer according to the present invention has a multi-crystal structure, and can exhibit excellent mechanical properties such as improved tensile strength, tear strength, and flexural modulus by reducing the ultra-low crystallinity content and increasing the relatively high crystallinity content.
[49]
[50]
(3) 15℃ < Te (elution temperature) < 50℃
[51]
As used herein, the elution temperature Te (Elution temperature) means the temperature of the highest point in the TREF or CFC elution curve expressed as the elution amount with respect to temperature (dC/dT).
[52]
In calculating Te, the starting point of each peak in the elution amount (dC/dT) graph with respect to temperature is defined as the point at which the polymer starts to elute based on the base line, and the end point of each peak is based on the baseline It can be defined as the point at which the elution of the polymer ends. At this time, if the end point and start point of the previous peak cannot be defined based on the baseline because the two peaks overlap, the point at which the peak eluting at a relatively low temperature begins to decrease after reaching the maximum point and then starts to increase again is the It is defined as the end point and the start point of the trailing peak. In addition, the peak expressed at -20°C to -10°C can be seen as a part of the peak appearing after -10°C appears at this position due to measurement limitations, and therefore, the peak appearing at this position is after -10°C It can be treated by including it in the peaks in
[53]
In the present specification, the meaning of single crystallinity means having only one peak except for the soluble fraction (SF, Soluble Fraction) at -20°C in the elution amount (dC/dT) graph with respect to temperature, and multiple crystallinity is at -20°C. It means having two or more peaks except for the soluble fraction of (SF, Soluble Fraction). In addition, in the present specification, when the polymer is multi-crystalline, Te (elution temperature) is the temperature of the peak of the peak in the CFC elution curve expressed as the elution amount (dC/dT), that is, only the highest point of the peak with a larger size is used as Te. do.
[54]
The olefin-based polymer according to an example of the present invention satisfies 15°C < Te (elution temperature) < 50°C, specifically 15°C ≤ Te (elution temperature) ≤ 40°C, and more specifically 20°C ≤ Te (elution temperature) ≤ 40 ℃ can be satisfied.
[55]
[56]
(4) Te (elution temperature) has a linear correlation with the density of the polymer, and satisfies Equation 1 below
[57]
The Te (elution temperature) has a linear correlation with the density of the polymer and satisfies Equation 1 below.
[58]
[Equation 1]
[59]
Te = 1,220×Density-A
[60]
In Equation 1, A satisfies the range of 1,031≤A≤1,039.
[61]
[62]
The olefin-based polymer according to an example of the present invention may further satisfy (5) a density (d) of 0.860 to 0.890 g/cc, and specifically 0.865 to 0.890 g/cc when measured according to ASTM D-792. and more specifically, 0.865 to 0.880 g/cc may be satisfied.
[63]
In addition, the olefin-based polymer according to an example of the present invention may further satisfy (6) a melt index (Melt Index, MI, 190°C, 2.16 kg load condition) of 0.1 dg/min to 10.0 dg/min, specifically 0.1 dg/min to 8.0 dg/min, more specifically 0.1 dg/min to 5.0 dg/min may be satisfied.
[64]
The melt index (MI) can be controlled by adjusting the amount of the catalyst used in the process of polymerizing the olefin-based polymer for the comonomer, and can affect the mechanical properties and impact strength, and moldability of the olefin-based polymer. .
[65]
In addition, the olefin-based polymer according to an example of the present invention may satisfy (7) a weight average molecular weight (Mw) of 70,000 to 500,000, specifically 70,000 to 300,000, and more specifically 70,000 to 200,000.
[66]
In addition, the olefin-based polymer according to an example of the present invention has a ratio (Mw/Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) (8) Molecular Weight Distribution (MWD) of 1.0 to 3.0 may be satisfied, specifically, 1.5 to 2.8, more specifically, 1.8 to 2.6. The olefin-based polymer according to an example of the present invention may exhibit a narrow molecular weight distribution by polymerization using a catalyst composition including two types of transition metal compounds having a characteristic structure.
[67]
In addition, the olefin-based polymer according to an example of the present invention has one single peak in the molecular weight distribution curve. The olefin-based polymer according to an example of the present invention is polymerized using a catalyst composition including two types of transition metal compounds to have multiple crystallinity and a single molecular weight distribution.
[68]
In general, the density of the olefin-based polymer is affected by the type and content of the monomer used during polymerization, the degree of polymerization, and the like. The olefin-based polymer of the present invention is polymerized using a catalyst composition including two types of transition metal compounds having a characteristic structure, and a large amount of comonomer can be introduced. may have a low density of
[69]
The olefin-based polymer may have a melting temperature (Tm) of 100° C. or less, specifically 80° C. or less, and more specifically 10° C. to 70° C. have.
[70]
The olefin-based polymer is an olefin-based monomer, specifically, an alpha-olefin-based monomer, a cyclic olefin-based monomer, a diene olefin-based monomer, a triene olefin-based monomer, and a styrene-based monomer, or any one homopolymer selected from It may be a copolymer of more than one species. More specifically, the olefin-based polymer may be a copolymer of ethylene and an alpha-olefin having 3 to 12 carbon atoms or 3 to 10 carbon atoms, and more specifically, a copolymer of ethylene and 1-octene.
[71]
The alpha-olefin comonomer 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, 1-aitocene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1,5 - It may include any one or a mixture of two or more selected from the group consisting of -pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.
[72]
More specifically, the olefin copolymer according to an example of the present invention may be a copolymer of ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4-methyl-1-pentene, or ethylene and 1-octene. And, more specifically, the olefin copolymer according to an example of the present invention may be a copolymer of ethylene and 1-octene.
[73]
When the olefin-based polymer is a copolymer of ethylene and alpha-olefin, the amount of the alpha-olefin is 90 wt% or less, more specifically 70 wt% or less, and even more specifically 5 wt% to 60 wt% based on the total weight of the copolymer. % by weight, even more specifically 20% to 50% by weight. When the alpha-olefin is included in the above range, it is easy to implement the above-described physical properties.
[74]
The olefin-based polymer according to an embodiment of the present invention having the above physical properties and structural characteristics is prepared through a continuous solution polymerization reaction in the presence of a metallocene catalyst composition including one or more transition metal compounds in a single reactor can be Accordingly, in the olefin-based polymer according to an embodiment of the present invention, a block is not formed in which two or more repeating units derived from any one of the monomers constituting the polymer in the polymer are linearly connected. That is, the olefin-based polymer according to the present invention does not contain a block copolymer, and is selected from the group consisting of a random copolymer, an alternating copolymer, and a graft copolymer. and, more specifically, may be a random copolymer.
[75]
Specifically, the olefin-based copolymer of the present invention includes the transition metal compound of Formula 1 and the transition metal compound of Formula 2 in an equivalent ratio of 1:5 to 1:10, specifically, in an equivalent ratio of 1:5 to 1:7 In the presence of a catalyst composition for olefin polymerization, it can be obtained by a manufacturing method comprising the step of polymerizing an olefinic monomer.
[76]
However, in the preparation of the olefin-based polymer according to an embodiment of the present invention, the scope of the structures of the following first transition metal compound and the second transition metal compound is not limited to a specific disclosed form, and is within the spirit and technical scope of the present invention. It is to be understood as including all modifications, equivalents and substitutions included.
[77]
[Formula 1]
[78]

[79]
In Formula 1,
[80]
R 1 is the same as or different from each other, and each independently represents a metal of a Group 4 metal substituted with hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl, silyl, alkylaryl, arylalkyl, or hydrocarbyl. a Lloyd radical, wherein the two R 1 may be connected to each other by an alkylidine radical including an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms to form a ring;
[81]
R 2 are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; aryl; alkoxy; aryloxy; an amido radical, wherein two or more of R 2 may be connected to each other to form an aliphatic ring or an aromatic ring;
[82]
R 3 are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; or an aliphatic or aromatic ring containing nitrogen, substituted or unsubstituted with an aryl radical, and when the substituents are plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;
[83]
M 1 is a Group 4 transition metal;
[84]
Q 1 and Q 2 are each independently halogen; alkyl having 1 to 20 carbon atoms; alkenyl; aryl; alkylaryl; arylalkyl; alkyl amido having 1 to 20 carbon atoms; aryl amido; or an alkylidene radical having 1 to 20 carbon atoms;
[85]
[Formula 2]
[86]

[87]
In Formula 2,
[88]
R 4 is the same as or different from each other, and each independently represents a metal of a Group 4 metal substituted with hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl, silyl, alkylaryl, arylalkyl, or hydrocarbyl. a Lloyd group, wherein the two R 1 may be connected to each other by an alkylidine including an alkyl having 1 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms to form a ring;
[89]
R 5 are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; aryl; alkoxy; aryloxy; and amido , two or more of R 2 may be connected to each other to form an aliphatic ring or an aromatic ring;
[90]
R 6 are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; or an aliphatic or aromatic ring containing nitrogen, substituted or unsubstituted with aryl, and when the substituents are a plurality, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;
[91]
M 2 is a Group 4 transition metal;
[92]
Q 3 and Q 4 are each independently halogen; alkyl having 1 to 20 carbon atoms; alkenyl; aryl; alkylaryl; arylalkyl; alkyl amido having 1 to 20 carbon atoms; aryl amido; or an alkylidene having 1 to 20 carbon atoms.
[93]
[94]
In addition, in another example of the present invention, in Formula 1, R 1 And R 2 Are the same as or different from each other, and each independently hydrogen; alkyl having 1 to 20 carbon atoms; aryl; or silyl,
[95]
R 3 are the same as or different from each other, and alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl; alkylaryl; arylalkyl; alkoxy having 1 to 20 carbon atoms; aryloxy; or amido; two or more adjacent R 3 of R 3 may be connected to each other to form an aliphatic or aromatic ring;
[96]
Q 1 and Q 2 are the same as or different from each other, and each independently halogen; alkyl having 1 to 20 carbon atoms; alkylamido having 1 to 20 carbon atoms; may be arylamido,
[97]
M 1 may be a Group 4 transition metal.
[98]
In addition, in Formula 2, 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; aryl; or silyl,
[99]
R 6 are the same as or different from each other, and alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl; alkylaryl; arylalkyl; alkoxy having 1 to 20 carbon atoms; aryloxy; or amido; Wherein R 6 in at least two R 6 are connected to each other can form a aliphatic or aromatic ring;
[100]
The Q 3 and Q 4 are the same as or different from each other, and each independently halogen; alkyl having 1 to 20 carbon atoms; alkylamido having 1 to 20 carbon atoms; may be arylamido,
[101]
M 2 may be a Group 4 transition metal.
[102]
[103]
In addition, in the transition metal compound represented by Formula 1 or Formula 2, the metal site is connected by a cyclopentadienyl ligand into which tetrahydroquinoline is introduced, and thus the Cp-MN angle is structurally narrow, and Q 1 - MQ 2 (Q 3 -MQ 4 ) has the characteristic of keeping the angle wide. In addition, Cp, tetrahydroquinoline, nitrogen and metal sites are sequentially linked by a ring bond to form a more stable and rigid pentagonal ring structure. Therefore, when these compounds are activated by reacting them with a cocatalyst such as methylaluminoxane or B(C 6 F 5 ) 3 , and then applied to olefin polymerization, characteristics such as high activity, high molecular weight and high copolymerizability are obtained even at high polymerization temperatures. It is possible to polymerize the olefinic polymer having.
[104]
Each of the substituents defined in the present specification will be described in detail as follows.
[105]
As used herein, the term 'hydrocarbyl group' is, unless otherwise stated, the number of carbon atoms consisting only of carbon and hydrogen, regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl or arylalkyl. It means a monovalent hydrocarbon group of 1-20.
[106]
As used herein, the term 'halogen' means fluorine, chlorine, bromine or iodine, unless otherwise noted.
[107]
The term 'alkyl' as used herein, unless otherwise stated, refers to a straight-chain or branched hydrocarbon residue.
[108]
As used herein, the term 'alkenyl' refers to a straight-chain or branched alkenyl group, unless otherwise specified.
[109]
The branched chain is 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; Or it may be an arylalkyl having 7 to 20 carbon atoms.
[110]
According to an example of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.
[111]
The alkylaryl group means an aryl group substituted by the alkyl group.
[112]
The arylalkyl group means an alkyl group substituted by the aryl group.
[113]
The ring (or heterocyclic group) refers to a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 carbon atoms and one or more hetero atoms, and may be a single ring or a condensed ring of two or more rings. In addition, the heterocyclic group may be unsubstituted or substituted with an alkyl group. Examples thereof include indoline and tetrahydroquinoline, but the present invention is not limited thereto.
[114]
The alkyl amino group refers to an amino group substituted by the alkyl group, and includes, but is not limited to, a dimethylamino group, a diethylamino group, and the like.
[115]
According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, etc., but is limited only to these examples. no.
[116]
The compound of Formula 1 may be at least one selected from the group consisting of the following Chemical Formulas 1-1 to 1-2, and the compound of Formula 2 may be at least one selected from the group consisting of the following Chemical Formula 2-1, but is not limited thereto. does not
[117]
[Formula 1-1]
[118]

[119]
[Formula 1-2]
[120]

[121]
[Formula 2-1]
[122]

[123]
[124]
In addition, it may be a compound having various structures within the ranges defined in Formulas 1 and 2 above.
[125]
[126]
The transition metal compound of Formula 1 and the transition metal compound of Formula 2 have a density of 0.850 g/cc to 0.865 g/cc, level, because a large amount of alpha-olefin as well as low-density polyethylene can be introduced due to the structural characteristics of the catalyst. of low-density polyolefin copolymers can be prepared. In addition, when the transition metal compound of Formula 1 and the transition metal compound of Formula 2 are used together in an equivalent ratio of 1:1 to 1:5, specifically 1:1 to 1:4, high molecular weight and narrow molecular weight distribution , and it is possible to prepare an olefin-based polymer having a low density.
[127]
[128]
The transition metal compounds of Formulas 1 and 2 may be prepared by the following method as an example.
[129]
[Scheme 1]
[130]

[131]
In Scheme 1, R 1 to R 3 , M 1 , Q 1 , and Q 2 are each as defined in Formula 1 above.
[132]
In addition, the transition metal compound of Formula 2 may be prepared by the following method as an example.
[133]
[Scheme 2]
[134]

[135]
In Scheme 2, R 4 to R 6 , M 2 , Q 3 , and Q 4 are as defined in Formula 2 above.
[136]
Formula 1 and Formula 2 may be prepared according to the method described in Korean Patent Publication No. 2007-0003071, and the entire contents of the patent document are included in the present specification.
[137]
The transition metal compound of Formula 1 and the transition metal compound of Formula 2 may be mixed alone or in addition to the transition metal compound of Formula 1 and the transition metal compound of Formula 2, a group represented by Formula 3, Formula 4, and Formula 5 In the form of a composition further comprising at least one of the catalyst compounds, it may be used as a catalyst for a polymerization reaction.
[138]
[Formula 3]
[139]
-[Al(R 7 )-O] a -
[140]
[Formula 4]
[141]
A(R 7 ) 3
[142]
[Formula 5]
[143]
[LH] + [W(D) 4 ] - or [L] + [W(D) 4 ] -
[144]
In Formulas 3 to 5,
[145]
R 7 may be the same as or different from each other, and are each independently selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
[146]
A is aluminum or boron,
[147]
D is each independently aryl having 6 to 20 carbons or alkyl having 1 to 20 carbons in which one or more hydrogen atoms may be substituted with a substituent, wherein the substituents are halogen, hydrocarbyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons and at least one selected from the group consisting of aryloxy having 6 to 20 carbon atoms,
[148]
H is a hydrogen atom,
[149]
L is a neutral or cationic Lewis acid,
[150]
W is a group 13 element,
[151]
a is an integer greater than or equal to 2;
[152]
Examples of the compound represented by Formula 3 include alkylaluminoxanes such as methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and two or more of the alkylaluminoxanes are mixed and modified alkylaluminoxane, and specifically may be methylaluminoxane and modified methylaluminoxane (MMAO).
[153]
Examples of the compound represented by Formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and specifically may be selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.
[154]
Examples of the compound represented by Formula 5 include triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, trimethylammoniumtetra (o,p-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetrapentafluorophenylboron, N,N -diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtetraphenylboron, dimethyl Anilinium tetrakis(pentafluorophenyl)borate, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra(p-tolyl)aluminum, tri Propylammoniumtetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammoniumtetra(p-trifluoromethylphenyl)aluminum, trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum , tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, diethylammoniumtetrapentatenttraphenylaluminum, triphenyl Phosphonium tetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, triphenylcarboniumtetra(p-trifluoromethylphenyl) ) boron or triphenylcarboniumtetrapentafluorophenylboron.
[155]
The catalyst composition is, as a first method, 1) contacting the first mixture of the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 with the compound represented by Formula 3 or Formula 4 to obtain a mixture step; and 2) adding the compound represented by Formula 5 to the mixture.
[156]
In addition, as a second method, the catalyst composition may be prepared by contacting the compound represented by Formula 3 with a first mixture of the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 as a second method. .
[157]
In the case of the first method among the methods for preparing the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2/the compound represented by Formula 3 or Formula 4 is 1/ It may be 5,000 to 1/2, specifically 1/1,000 to 1/10, and more specifically 1/500 to 1/20. When the molar ratio of the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 to the compound represented by Formula 3 or Formula 4 exceeds 1/2, the amount of the alkylating agent is very small and the metal compound There is a problem that the alkylation does not proceed completely, and when the molar ratio is less than 1/5,000, the metal compound is alkylated, but due to a side reaction between the remaining excess alkylating agent and the activator, which is the compound of Formula 5, the alkylated metal compound There is a problem that the activation of the is not completely done. In addition, the molar ratio of the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2/the compound represented by Formula 5 may be 1/25 to 1, specifically 1/10 to 1 day may be, and more specifically, 1/5 to 1. When the molar ratio of the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2/compound represented by Formula 5 exceeds 1, the amount of the activator is relatively small, so that the activation of the metal compound is difficult. If the molar ratio is less than 1/25, the activation of the metal compound is completely achieved,
[158]
In the case of the second method among the methods for preparing the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2/compound represented by Formula 3 is 1/10,000 to 1/ It may be 10, specifically 1/5,000 to 1/100, and more specifically, 1/3,000 to 1/500. When the molar ratio exceeds 1/10, the amount of the activator is relatively small, so the activation of the metal compound may not be completely achieved, and thus the activity of the resulting catalyst composition may decrease. If the molar ratio is less than 1/10,000, the activation of the metal compound is completely achieved, but the cost of the catalyst composition may not be economical or the purity of the resulting polymer may be deteriorated with the excess amount of activator remaining.
[159]
In preparing the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene or toluene may be used as the reaction solvent.
[160]
In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a supported form on a carrier.
[161]
The carrier may be used without any particular limitation as long as it is used as a carrier in a metallocene-based catalyst. Specifically, the carrier may be silica, silica-alumina or silica-magnesia, and any one or a mixture of two or more thereof may be used.
[162]
Among them, when the carrier is silica, since the functional group of the silica carrier and the metallocene compound of Formula 1 chemically forms a bond, there is almost no catalyst released from the surface during the olefin polymerization process. As a result, it is possible to prevent the occurrence of fouling in which the reactor wall or polymer particles are agglomerated during the manufacturing process of the olefin-based polymer. In addition, the olefin-based polymer prepared in the presence of the catalyst including the silica carrier has excellent particle shape and apparent density of the polymer.
[163]
More specifically, the carrier may be high-temperature dried silica or silica-alumina containing a siloxane group having high reactivity on the surface through a method such as high-temperature drying.
[164]
The carrier may further include an oxide, carbonate, sulfate or nitrate component such as Na 2 O, K 2 CO 3 , BaSO 4 or Mg(NO 3 ) 2 .
[165]
The polymerization reaction for polymerizing the olefinic monomer may be accomplished by a conventional process applied to polymerization of the olefinic monomer, such as continuous solution polymerization, bulk polymerization, suspension polymerization, slurry polymerization, or emulsion polymerization.
[166]
The polymerization reaction of the olefin monomer may be performed under an inert solvent, and the inert solvent includes benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, but not limited thereto.
[167]
The polymerization of the olefin-based polymer may be carried out by reacting at a temperature of about 25 to about 500° C. and a pressure of about 1 to about 100 kgf/cm 2 .
[168]
Specifically, the polymerization of the polyolefin may be carried out at a temperature of about 25 °C to about 500 °C, specifically 80 °C to 250 °C, more preferably 100 °C to 200 °C. In addition, the reaction pressure during polymerization is 1 kgf/cm 2 to 150 kgf/cm 2 , preferably 1 kgf/cm 2 to 120 kgf/cm 2 , more preferably 5 kgf/cm 2 to 100 kgf/cm 2 can be
[169]
[170]
Since the olefin-based polymer of the present invention has improved physical properties, it is for blow molding and extrusion in various fields and uses such as materials for automobiles, electric wires, toys, textiles, medical products, etc. It is useful for molding or injection molding, and in particular, it can be usefully used for automobiles requiring excellent impact strength.
[171]
In addition, the olefin-based polymer of the present invention may be usefully used in the production of a molded article.
[172]
Specifically, the molded article may be a blow molding molded article, an inflation molded article, a cast molded article, an extrusion laminate molded article, an extrusion molded article, an expanded molded article, an injection molded article, a sheet, a film, a fiber, a monofilament, or a nonwoven fabric.
Modes for carrying out the invention
[173]
Example
[174]
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.
[175]
[176]
Preparation Example 1: Preparation of transition metal compound 1
[177]

[178]
(1) 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (8-(2,3,4,5- Preparation of tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline)
[179]
(i) Preparation of lithium carbamate
[180]
1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were placed in a shlenk flask. The Schlenk flask was immersed in a -78°C low-temperature bath made of dry ice and acetone and stirred for 30 minutes. Then, n-BuLi (39.3 mL, 2.5 M, 98.24 mmol) was injected into a syringe under a nitrogen atmosphere, and a pale yellow slurry was formed. Then, after stirring the flask for 2 hours, the temperature of the flask was raised to room temperature while removing the butane gas produced. The flask was again immersed in a low temperature bath at -78° C. to lower the temperature, and then CO 2 gas was introduced. As the carbon dioxide gas was added, the slurry disappeared and became a transparent solution. The flask was connected to a bubbler and the temperature was raised to room temperature while removing carbon dioxide gas. After that, excess CO 2 gas and solvent were removed under vacuum . After moving the flask to a dry box, pentane was added, stirred vigorously, and filtered to obtain lithium carbamate, a white solid compound. The white solid compound is coordinated with diethyl ether. In this case, the yield is 100%.
[181]
1 H NMR(C 6 D 6 , C 5 D 5 N): δ 1.90 (t, J = 7.2 Hz, 6H, ether), 1.50 (br s, 2H, quin-CH 2 ), 2.34 (br s, 2H) , quin-CH 2 ), 3.25 (q, J = 7.2 Hz, 4H, ether), 3.87 (br, s, 2H, quin-CH 2 ), 6.76 (br d, J = 5.6 Hz, 1H, quin-CH ) ppm
[182]
13 C NMR (C 6 D 6 ): δ 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57, 142.04, 163.09 (C=O) ppm
[183]
(ii) Preparation of 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline
[184]

[185]
The lithium carbamate compound (8.47 g, 42.60 mmol) prepared in step (i) was placed in a Schlenk flask. Then, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were sequentially added. The Schlenk flask was immersed in a low temperature bath at -20°C made of acetone and a small amount of dry ice and stirred for 30 minutes, and then t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of the reaction mixture changed to red. Stirring was continued for 6 hours while maintaining -20°C. A solution of CeCl 3 ·2LiCl dissolved in tetrahydrofuran (129 mL, 0.33 M, 42.60 mmol) and tetramethylcyclopentinone (5.89 g, 42.60 mmol) were mixed in a syringe, and then put into a flask under a nitrogen atmosphere. The temperature of the flask was slowly raised to room temperature, and after 1 hour, the thermostat was removed and the temperature was maintained at room temperature. Then, after adding water (15 mL) to the flask, ethyl acetate was added thereto and filtered to obtain a filtrate. After transferring the filtrate to a separatory funnel, hydrochloric acid (2 N, 80 mL) was added thereto, and the mixture was shaken for 12 minutes. Then, after neutralization by adding a saturated aqueous sodium hydrogen carbonate solution (160 mL), the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to remove moisture, filtered, and the filtrate was taken to remove the solvent. The obtained filtrate was purified by column chromatography using a solvent of hexane and ethyl acetate (v/v, 10:1) to obtain a yellow oil. The yield was 40%.
[186]
1 H NMR(C 6 D 6 ): δ 1.00 (br d, 3H, Cp-CH 3 ), 1.63 - 1.73 (m, 2H, quin-CH 2 ), 1.80 (s, 3H, Cp-CH 3 ), 1.81 (s, 3H, Cp-CH 3 ), 1.85 (s, 3H, Cp-CH 3 ), 2.64 (t, J = 6.0 Hz, 2H, quin-CH 2 ), 2.84 - 2.90 (br, 2H, quin -CH 2 ), 3.06 (br s, 1H, Cp-H), 3.76 (br s, 1H, NH), 6.77 (t, J = 7.2 Hz, 1H, quin-CH), 6.92 (d, J = 2.4 Hz, 1H, quin-CH), 6.94 (d, J = 2.4 Hz, 1H, quin-CH) ppm
[187]
[188]
(2) [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η 5 , κ -N] titanium dimethyl ([(1,2,3,4-Tetrahydroquinolin- Preparation of 8-yl)tetramethylcyclopentadienyl-eta5,kapa-N]titanium dimethyl)
[189]

[190]
(i) Preparation of [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η 5 , κ -N]dilithium compound
[191]
8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (8.07 g) prepared through step (1) in a dry box , 32.0 mmol) and 140 mL of diethyl ether were placed in a round flask, the temperature was lowered to -30°C, and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was slowly added with stirring. The reaction was carried out for 6 hours while raising the temperature to room temperature. After that, it was filtered while washing with diethyl ether several times to obtain a solid. A vacuum was applied to remove the remaining solvent to obtain a dilithium compound (9.83 g) as a yellow solid. The yield was 95%.
[192]
1 H NMR(C 6 D 6 , C 5 D 5 N): δ 2.38 (br s, 2H, quin-CH 2 ), 2.53 (br s, 12H, Cp-CH 3 ), 3.48 (br s, 2H, quin-CH 2 ), 4.19 (br s, 2H, quin-CH 2 ), 6.77 (t, J = 6.8 Hz, 2H, quin-CH), 7.28 (br s, 1H, quin-CH), 7.75 (brs) , 1H, quin-CH) ppm
[193]
[194]
(ii) (1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl- η 5 , κ -N] Preparation of titanium dimethyl
[195]
In a dry box, TiCl 4 ·DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL) were placed in a round flask, and while stirring at -30°C, MeLi (21.7 mL, 31.52 mmol, 1.4 M) was slowly added thereto. After stirring for 15 minutes, the [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η 5 , κ -N]dilithium compound prepared in step (i) ( 5.30 g, 15.76 mmol) was placed in a flask. While raising the temperature to room temperature, the mixture was stirred for 3 hours. After the reaction was completed, vacuum was applied to remove the solvent, dissolved in pentane, and filtered to obtain a filtrate. When pentane was removed by vacuum, a dark brown compound (3.70 g) was obtained. The yield was 71.3%.
[196]
1 H NMR(C 6 D 6 ): δ 0.59 (s, 6H, Ti-CH 3 ), 1.66 (s, 6H, Cp-CH 3 ), 1.69 (br t, J = 6.4 Hz, 2H, quin-CH 2 ), 2.05 (s, 6H, Cp-CH 3 ), 2.47 (t, J = 6.0 Hz, 2H, quin-CH 2 ), 4.53 (m, 2H, quin-CH 2 ), 6.84 (t, J = 7.2 Hz, 1H, quin-CH), 6.93 (d, J =7.6 Hz, quin-CH), 7.01 (d, J =6.8 Hz, quin-CH) ppm
[197]
13 C NMR (C 6 D 6 ): δ 12.12, 23.08, 27.30, 48.84, 51.01, 119.70, 119.96, 120.95, 126.99, 128.73, 131.67, 136.21 ppm
[198]
[199]
Preparation Example 2: Preparation of transition metal compound 2
[200]

[201]
(1) Preparation of 2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline
[202]
Through the same method as in (1) of Preparation Example 1, except that 2-methyl indoline was used instead of 1,2,3,4-tetrahydroquinoline in (1) of Preparation Example 1, 2 -Methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline was prepared. The yield was 19%.
[203]
1 H NMR (C 6 D 6 ): δ 6.97 (d, J=7.2 Hz, 1H, CH), δ 6.78 (d, J=8 Hz, 1H, CH), δ 6.67 (t, J=7.4 Hz, 1H) , CH), δ 3.94 (m, 1H, quinoline-CH), δ 3.51 (br s, 1H, NH), δ 3.24-3.08 (m, 2H, quinoline-CH 2 , Cp-CH), δ 2.65 (m) , 1H, quinoline-CH 2 ), δ 1.89(s, 3H, Cp-CH 3 ), δ 1.84(s, 3H, Cp-CH 3 ), δ 1.82(s, 3H, Cp-CH 3 ), δ 1.13 (d, J=6Hz, 3H, quinoline-CH 3 ), δ 0.93(3H, Cp-CH 3 ) ppm.
[204]
[205]
(2) [(2-Methylindolin-7-yl)tetramethylcyclopentadienyl-eta5,kappa-N]titanium dimethyl ([(2-Methylindolin-7-yl)tetramethylcyclopentadienyl-eta5,kapa-N] production of titanium dimethyl)
[206]
(i) 2-methyl-7-(2,3 instead of 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline ,4,5-tetramethyl-1,3-cyclopentadienyl)-indoline (2.25 g, 8.88 mmol) through the same method as (2) (i) of Preparation Example 1, except that 0.58 equivalents of diethyl ether-coordinated dilithium salt compound (compound 4 g) was obtained (1.37 g, 50 %).
[207]
1 H NMR (Pyridine-d8): δ 7.22 (br s, 1H, CH), δ 7.18 (d, J=6Hz, 1H, CH), δ 6.32 (t, 1H, CH), δ 4.61 (brs, 1H) , CH), δ 3.54 (m, 1H, CH), δ 3.00 (m, 1H, CH), δ 2.35-2.12 (m , 13H, CH, Cp-CH3), δ 1.39 (d, indoline-CH3) ppm .
[208]
[209]
(ii) A titanium compound was prepared in the same manner as in (2)(ii) of Preparation Example 1 with the dilithium salt compound (compound 4g) (1.37 g, 4.44 mmol) prepared in (i).
[210]
1 H NMR (C 6 D 6 ): δ 7.01-6.96 (m, 2H, CH), δ 6.82 (t, J=7.4 Hz, 1H, CH), δ
[211]
4.96(m, 1H, CH), δ 2.88(m, 1H, CH), δ 2.40(m, 1H, CH), δ 2.02(s, 3H, Cp-CH 3 ), δ 2.01(s, 3H, Cp -CH 3 ), δ 1.70(s, 3H, Cp-CH 3 ), δ 1.69(s, 3H, Cp-CH 3 ), δ 1.65 (d, J=6.4Hz, 3H, indoline-CH 3 ), δ 0.71 (d, J=10 Hz, 6H, TiMe 2 -CH 3 ) ppm.
[212]
[213]
Example 1
[214]
After the 1.5L continuous process reactor was charged with hexane solvent (7 kg/h) and 1-octene (1.15 kg/h), the temperature at the top of the reactor was preheated to 150°C. Triisobutylaluminum compound (0.06 mmol/min), the transition metal compound 1 obtained in Preparation Example 1, and the transition metal compound 2 obtained in Preparation Example 2 were mixed in a molar ratio of 1:5. A mixture of a transition metal compound (0.53 μmol) /min), and dimethylanilinium tetrakis(pentafluorophenyl)borate cocatalyst (1.59 μmol/min) were simultaneously introduced into the reactor. Then, ethylene (0.87 kg/h) was introduced into the reactor, and the copolymer was obtained by maintaining the reaction temperature at 150° C. for at least 30 minutes in a continuous process at a pressure of 89 bar. After drying in a vacuum oven for more than 12 hours, physical properties were measured.
[215]
[216]
Examples 2 to 5
[217]
A copolymer was obtained by performing a copolymerization reaction in the same manner as in Example 1, except that the amount of reactants and the polymerization temperature were adjusted as shown in Table 1 below.
[218]
[219]
Comparative Example 1
[220]
Dow's EG8150 was purchased and used.
[221]
[222]
Comparative Example 2
[223]
A copolymer was obtained by performing a copolymerization reaction using the same method as in Example 1, except that the amount of reactants and the polymerization temperature were adjusted as shown in Table 1 using only transition metal compound 2 as a catalyst.
[224]
[225]
Comparative Examples 3 and 4
[226]
The copolymerization reaction was carried out using two transition metal catalysts in the same manner as in Example 1, and the ratio of the two transition metals, the ratio of the catalyst and the cocatalyst, and the reaction temperature and the amount of comonomer were respectively changed as shown in Table 1 below. The reaction proceeded to obtain a copolymer.
[227]
[228]
[Table 1]
Catalyst ratio (transition metal compound 1:2) Catalyst (μmol/min) Cocatalyst (μmol/min) TiBAl (mmol/min) Ethylene (kg/h) Hexane (kg/h) 1-octene (kg/h) Reaction temperature (℃)
Example 1 1:5 0.53 1.59 0.06 0.87 7.0 1.15 150
Example 2 1:5 0.53 1.59 0.06 0.87 7.0 1.23 146
Example 3 1:5 0.70 2.10 0.06 0.87 7.0 1.20 150
Example 4 1:5 0.43 1.50 0.06 0.87 7.0 1.23 146
Example 5 1:5 0.73 1.59 0.06 0.87 7.0 1.05 150
Comparative Example 2 0:1 0.7 2.1 0.09 0.87 7.0 1.25 149
Comparative Example 3 1.4:1 0.3 0.9 0.05 0.87 7.0 1.05 148
Comparative Example 4 1:3 0.42 1.26 0.05 0.87 7.0 1.10 149
[229]
Experimental example
[230]
The copolymers of Examples 1 to 5 and Comparative Examples 1 to 4 were evaluated for physical properties according to the following method, and are shown in Table 2 below.
[231]
[232]
1) Soluble Fraction, Te (elution temperature), T(90), T(50)
[233]
As the measuring equipment, PolymerChar's CFC was used. First, a solution of the copolymer using o-dichlorobenzene as a solvent was completely dissolved in an oven in a CFC analyzer at 130° C. for 60 minutes, poured into a TREF column adjusted to 135° C., cooled to 95° C., and stabilized there for 45 minutes. The temperature of the TREF column was then lowered to -20°C at a rate of 0.5°C/min, and then held at -20°C for 10 minutes. Then, the amount of elution (mass %) was measured using an infrared spectrophotometer. Then, the operation of raising the temperature rise of the TREF column at a rate of 20 °C/mi to a preset temperature and maintaining the temperature at the temperature reached for a preset time (i.e., about 27 minutes) was performed when the temperature of the TREF was 130 °C. Repeat until this, and the amount (mass %) of the fraction eluted during each temperature range was measured.
[234]
The content of the ultra-low crystallinity region means the content of the fraction eluted at -20°C or less, and the elution temperature (Te) was measured as the temperature of the highest point of the peak.
[235]
2) Density of the polymer
[236]
Measured by ASTM D-792.
[237]
3) Melt Index (MI) of polymer
[238]
It was measured according to ASTM D-1238 [Condition E, MI 10 (190° C., 10 kg load), MI 2.16 (190° C., 2.16 kg load)].
[239]
4) Weight average molecular weight (Mw) and molecular weight distribution (MWD)
[240]
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were respectively measured using gel permeation chromatography (GPC), and the molecular weight distribution was calculated by dividing the weight average molecular weight by the number average molecular weight.
[241]
- Column: PL Olexis
[242]
- Solvent: TCB (Trichlorobenzene)
[243]
- Flow rate: 1.0 ml/min
[244]
- Sample concentration: 1.0 mg/ml
[245]
- Injection volume: 200 μl
[246]
- Column temperature: 160℃
[247]
- Detector: Agilent High Temperature RI detector
[248]
- Standard: Polystyrene (corrected by cubic function)
[249]
5) Melting point of polymer (Tm)
[250]
It was obtained using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 6000) manufactured by PerKinElmer. That is, after increasing the temperature to 200°C, holding it at that temperature for 1 minute, then lowering it to -100°C, and increasing the temperature again, the top of the DSC curve was used as the melting point. At this time, the rate of temperature rise and fall is 10° C./min, and the melting point is obtained while the second temperature rises.
[251]
6) Determination of comonomer content
[252]
Take 50 mg of the sample, put it in a vial, add 1 mL of TCE-d2 solvent, melt the sample completely with a heat gun, and transfer it to an NMR tube. 1H NMR was measured at Number of Scan (ns) = 2048 (3h 30min), measuring temperature 393 K, and then prepared by first reprecipitating the polymer before NMR analysis to remove residual 1-octene or 1-butene that may be present in the specimen. did. Specifically, 1 g of the polymer was completely dissolved in chloroform at 70° C., and the resulting polymer solution was slowly poured into 300 ml of methanol with stirring to reprecipitate the polymer, and then the reprecipitated polymer was vacuum dried at room temperature. The above process was repeated once more to obtain a polymer from which residual 1-octene was removed.
[253]
A 50 mg specimen of the polymer obtained above was dissolved in 1 ml of TCE-d2 solvent. Using the Bruker AVANCEⅢ 500MHz NMR equipment, 2048 measurements were made at room temperature with an acquisition time of 3 seconds and a pulse angle of 30°. The comonomer content (%[1-C8]) was calculated using the integral value of the ethylene, 1-butene, and 1-octene peaks in the range of 0.5 to 1.5 ppm. The number of double bonds was calculated based on the integral value of the double bonds in the 4.5-6.0 ppm region. Macromolecules 2014, 47, 3782-3790 were referred to.
[254]
[Table 2]
Density (g/mL) MI 2.16 (dg/min) Mw (g/mol) MWD Number of GPC peaks Tm(℃) %[1-C8]
Example 1 0.871 0.44 135098 2.35 One 56.6 34.1
Example 2 0.870 0.28 140790 2.33 One 56.1 35.3
Example 3 0.866 1.23 112341 2.29 One 51.0 39.0
Example 4 0.868 0.12 156116 2.33 One 53.6 37.0
Example 5 0.874 3.6 90391 2.32 One 61.4 31.6
Comparative Example 1 0.869 0.47 138442 2.18 One 60.1 35.7
Comparative Example 2 0.868 0.54 128563 2.33 One 50.3 36.0
Comparative Example 3 0.870 0.50 126936 2.31 One 54.5 32.1
Comparative Example 4 0.870 0.52 128420 2.30 One 54.7 32.1
[255]
[Table 3]
Number of CFC peaks crystal structure Te(℃) SF (%) T(90)(℃) T(50)(℃) T(90)-T(50)
Example 1 2 multiple crystal 28.5 0.7 34.5 27.0 7.5
Example 2 2 multiple crystal 27.1 1.3 33.5 26.0 7.5
Example 3 2 multiple crystal 22.2 3.1 28.0 21.5 6.5
Example 4 2 multiple crystal 25.1 1.9 32.0 25.0 7.0
Example 5 2 multiple crystal 32.1 0.3 36.5 30.5 6.0
Comparative Example 1 One single crystal 29.3 1.0 34.5 25.0 9.5
Comparative Example 2 One single crystal 19.9 0.3 28.5 19.5 9.0
Comparative Example 3 2 multiple crystal 14.4 0.7 38.0 21.0 17
Comparative Example 4 2 multiple crystal 27.4 1.1 34.5 25.0 9.5
[256]
On the other hand, the CFC dissolution curves of Example 1 and Comparative Example 1 are shown in FIG. 1, and a graph showing the correlation between the density of the polymers of Examples 1 to 5, and Comparative Examples 1 to 4 and Te (elution temperature) is shown. 2 is shown. Referring to FIG. 1 , it can be seen that Example 1 has two peaks in the CFC elution curve, and it can be seen that the width of the peak is narrower than that of Comparative Example 1. Since the width of the peak is narrow, as can be seen from Table 2, it can be seen that the Example has T(90)-T(50) less than 8, unlike the Comparative Example. In Figures 5 to 5, it can be seen that the density and Te (elution temperature) have a linear correlation, and the relationship satisfies Equation (1). On the other hand, Comparative Examples 1 to 3 do not satisfy Equation 1, and Comparative Example 4 satisfies Equation 1, but T(90)-T(50) is 8 or more.
[257]
Meanwhile, the molecular weight distribution curves measured by GPC of Example 1 and Comparative Example 1 are shown in FIG. 3 , and it can be confirmed that both Example 1 and Comparative Example 1 have one single peak. 1 and 2, it can be seen that Comparative Example has a single molecular weight distribution and crystallinity distribution, whereas the Example has a single molecular weight distribution and multiple crystallinity distribution.
[258]
[259]
Experimental Example 2
[260]
For the olefinic polymers of Example 1 and Comparative Examples 1 to 4, specimens were prepared by injection molding at a temperature of 200° C. using an injection machine, and after leaving them in a constant temperature and humidity room for 1 day, tensile strength and flexural strength according to the following method The strength and flexural modulus were measured and shown in Table 3 below.
[261]
1) Tensile strength and tear strength of olefin-based polymer
[262]
Measurements were made according to ASTM D638 using an INSTRON 3365 instrument.
[263]
2) Flexural modulus of olefin-based polymer
[264]
Measurements were made according to ASTM D790 using an INSTRON 3365 instrument.
[265]
3) Hardness of olefin-based polymer (shore A)
[266]
Hardness was measured according to ASTM D2240 standard using TECLOCK's GC610 STAND for Durometer and Mitutoyo's Shore Durometer Type A.
[267]
[Table 4]
Density (g/mL) MI 2.16 (dg/min) Tm(℃) MWD Tensile strength (MPa) Tear strength (kN/m) Flexural modulus (MPa) Hardness (Shore A)
Example 1 0.871 0.44 56.6 2.35 11.73 270. .67 14.6 70.4
Comparative Example 1 0.869 0.47 60.1 2.24 11.45 24.85 12.0 67.74
Comparative Example 2 0.868 0.54 50.3 2.33 9.00 23.45 12.2 66.76
Comparative Example 3 0.870 0.50 54.5 2.31 9.98 24.06 12.44 69.61
Comparative Example 4 0.870 0.52 54.7 2.30 10.46 23.81 13.752 68.83
[268]
Referring to Table 4, it can be seen that Example 1 is improved in tensile strength, tear strength, flexural modulus, and hardness compared to Comparative Examples 1 to 4 having a similar density and MI.
[269]
[270]
Claims
[Claim 1]
(1) Cross-fractionation chromatography (CFC) has two peaks except for the soluble fraction (SF, Soluble Fraction) at -20 ° C in the temperature range of -20 ° C to 120 ° C when measured, and T (90 )-T(50)<8.0°C (T(90) is the temperature at which 90% by weight of the olefinic polymer is eluted, and T(50) is the temperature at which 50% by weight of the olefinic polymer is eluted); (2) the soluble fraction (SF, Soluble Fraction) at -20 ℃ on cross-fractionation chromatography (CFC, Cross-fractionation Chromatography) 10% by weight or less; (3) 15°C < Te (elution temperature) < 50°C; and (4) Te (elution temperature) has a linear correlation with the density of the polymer, satisfies Equation 1 below, and is a polycrystalline olefinic polymer. [Equation 1] Te = 1,220 × density-A (1,031≤A≤1,039)
[Claim 2]
The olefinic polymer according to claim 1, wherein the olefinic polymer further satisfies (5) a density (d) of 0.860 to 0.890 g/cc.
[Claim 3]
The olefinic polymer according to claim 1, wherein the olefinic polymer further satisfies (5) a density of 0.865 to 0.880 g/cc.
[Claim 4]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer further satisfies (6) a melt index (Melt Index, MI, 190°C, 2.16 kg load condition) of 0.1 dg/min to 10.0 dg/min.
[Claim 5]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer further satisfies (7) a weight average molecular weight (Mw) of 70,000 to 500,000.
[Claim 6]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer further satisfies (8) a molecular weight distribution (MWD) of 1.0 to 3.0.
[Claim 7]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer has a melting temperature (Tm) of 100° C. or less obtained from a DSC curve obtained by (9) differential scanning calorimetry (DSC) measurement.
[Claim 8]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer is a copolymer of ethylene and an alpha-olefin comonomer having 3 to 12 carbon atoms.
[Claim 9]
9. The method of claim 8, wherein the alpha-olefin comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-unde. cene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4 -Olefin comprising any one or a mixture of two or more selected from the group consisting of butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene based polymer.
[Claim 10]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer is a copolymer of ethylene and 1-octene.
[Claim 11]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer exhibits a single molecular weight distribution having one peak as measured by GPC.
[Claim 12]
According to claim 1, wherein the olefin-based polymer is an olefin-based polymer in the presence of a catalyst composition for olefin polymerization comprising the transition metal compound of Formula 1 and the transition metal compound of Formula 2 in an equivalent ratio of 1:5 to 1:7, Olefin-based polymer, which is obtained by a manufacturing method comprising the step of polymerizing a monomer: [Formula 1] In Formula 1, R 1 Are the same as or different from each other, and each independently hydrogen, alkyl having 1 to 20 carbon atoms, A metalloid radical of a Group 4 metal substituted with alkenyl, aryl, silyl, alkylaryl, arylalkyl, or hydrocarbyl having 2 to 20 carbon atoms , wherein the two R 1 are alkyl having 1 to 20 carbon atoms or 6 to carbon atoms may be linked to each other by an alkylidine radical comprising 20 aryl radicals to form a ring; R 2 are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; aryl; alkoxy; aryloxy; an amido radical, wherein two or more of R 2 may be connected to each other to form an aliphatic ring or an aromatic ring; R 3are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; or an aliphatic or aromatic ring containing nitrogen, substituted or unsubstituted with an aryl radical, and when the substituents are plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring; M 1 is a Group 4 transition metal; Q 1 and Q 2 are each independently halogen; alkyl having 1 to 20 carbon atoms; alkenyl; aryl; alkylaryl; arylalkyl; alkyl amido having 1 to 20 carbon atoms; aryl amido; or an alkylidene radical having 1 to 20 carbon atoms; [Formula 2] In Formula 2, R 4 Are the same as or different from each other, and each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl, silyl, alkylaryl, arylalkyl, or hydro It is a metalloid radical of a Group 4 metal substituted with carbyl, wherein the two R 1 are connected to each other by an alkylidine radical including an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms to form a ring. there is; R 5 are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; aryl; alkoxy; aryloxy; is an amido radical, wherein R two or more of them may be linked to each other to form an aliphatic ring or an aromatic ring; R 6 are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; or an aliphatic or aromatic ring containing nitrogen, substituted or unsubstituted with an aryl radical, and when the substituents are plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring; M 2 is a Group 4 transition metal; Q 3 and Q 4 are each independently halogen; alkyl having 1 to 20 carbon atoms; alkenyl; aryl; alkylaryl; arylalkyl; alkyl amido having 1 to 20 carbon atoms; aryl amido; or an alkylidene radical having 1 to 20 carbon atoms.
[Claim 13]
The olefin-based polymer according to claim 12, wherein the olefin-based polymer is prepared by a continuous solution polymerization reaction using a continuous stirred tank reactor in the presence of the catalyst composition for olefin polymerization.