Title of Invention: Olefin-based polymer
technical field
[One]
[Citation with related applications]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0082135 dated July 03, 2020, 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 high mechanical rigidity introduced by a highly crystalline region.
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 the molecule. As a result, it has been difficult to use polyolefins by blending them with polar resins or metals or by laminating 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 grafting 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]
Also, as another method, there is known a method of polymerization in the presence of a metallocene catalyst comprising a transition metal compound such as zircononocene dichloride and an organoaluminum oxy compound (aluminoxane). 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, by using a metallocene compound having a ligand of an uncrosslinked cyclopentadienyl group, a crosslinked or uncrosslinked bisindenyl group, or an ethylene bridged unsubstituted indenyl group/fluorenyl group as a catalyst, a polyolefin containing a polar group is prepared. As the method, a method using a metallocene catalyst is also known. However, these methods have a disadvantage in that the polymerization activity is very low. For this reason, although a method of protecting a polar group with a protecting group has been implemented, when a protecting group is introduced, the protecting group must be removed again after the reaction, thereby complicating the process.
[10]
Ansa-metallocene (ansa-metallocene) compound is an organometallic compound including two ligands connected to each other by a bridge group, rotation of the ligand is prevented by the bridge group, 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 an 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 to be solved by the present invention is to provide a low-density olefin-based polymer having high mechanical rigidity by introducing a highly crystalline region obtained by polymerizing an olefinic monomer by introducing hydrogen gas using a transition metal compound catalyst.
means of solving the problem
[15]
In order to solve the above problems, the present invention provides an olefin-based polymer satisfying the requirements of the following (1) to (5).
[16]
(1) Melt index (MI, 190 °C, load condition of 2.16 kg): 0.1 to 10.0 g/10 min;
[17]
(2) density (d): 0.875 to 0.895 g/cc;
[18]
(3) 0.5 J/g≤dH(100)≤3.0 J/g, and 1.0 J/g≤dH(90)≤6.0 ​​J/g in differential scanning calorimetry precision measurement (SSA);
[19]
(4) 15≤T(90)-T(50)≤30 in differential scanning calorimetry precision measurement (SSA), and 50°C≤T(50)≤75°C;
[20]
(5) a melting point (Tm) measured by differential scanning calorimetry (DSC) of 55°C≤Tm≤80°C;
[21]
where T(50) and T(90) are respectively the temperatures at which 50% and 90% of the temperature-heat capacity curve is fractionated from the differential scanning calorimetry precision measurement (SSA) measurement result, respectively, and dH(90) is It is the enthalpy of melting at 90°C or higher, and dH(100) represents the melting enthalpy at 100°C or higher.
Effects of the Invention
[22]
The olefin-based polymer according to the present invention is a low-density olefin-based polymer and exhibits high mechanical rigidity by introducing a high crystallinity region.
Brief description of the drawing
[23]
1 is a graph of T(50) versus density for the polymers of Examples 1-6 and the polymers of Comparative Examples 1 and 2.
[24]
FIG. 2 is a graph showing the results of measurement by differential scanning calorimetry (SSA) for the polymers of Example 5 and Comparative Example 2. FIG.
Best mode for carrying out the invention
[25]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[26]
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.
[27]
As used herein, the term "polymer" means 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" (which is commonly 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.
[28]
[29]
The olefin-based polymer according to the present invention satisfies the requirements of the following (1) to (5).
[30]
(1) Melt index (MI, 190 °C, load condition of 2.16 kg): 0.1 to 10.0 g/10 min; (2) density (d): 0.875 to 0.895 g/cc; (3) 0.5 J/g≤dH(100)≤3.0 J/g, and 1.0 J/g≤dH(90)≤6.0 ​​J/g in differential scanning calorimetry precision measurement (SSA); (4) 15≤T(90)-T(50)≤30 in differential scanning calorimetry precision measurement (SSA), and 50°C≤T(50)≤75°C; (5) The melting point (Tm) measured by differential scanning calorimetry (DSC) is 55 ℃ ≤ Tm ≤ 80 ℃.
[31]
The T(50) and T(90) are respectively the temperatures at which 50% and 90% of the temperature-heat capacity curve is fractionated from the differential scanning calorimetry precision measurement (SSA) measurement result, respectively, and dH(90) is It is the enthalpy of melting at 90°C or higher, and dH(100) represents the melting enthalpy at 100°C or higher.
[32]
The olefin-based polymer according to the present invention has a low density, and a high crystallinity region is introduced compared to a conventional olefin-based polymer, so that it has the same level of density and melt index (Melt Index, MI, 190°C, 2.16 kg load condition). , shows higher tensile strength, flexural modulus and hardness. The olefin-based polymer according to the present invention is prepared by a manufacturing method comprising the step of polymerizing an olefin-based monomer by introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization, and has high crystallinity according to hydrogen gas input during polymerization. The region is introduced to show excellent mechanical rigidity.
[33]
[34]
The melt index (MI) can be adjusted by controlling the amount of the catalyst used in the process of polymerizing the olefin-based polymer for the comonomer, and affects the mechanical properties and impact strength, and moldability of the olefin-based polymer. In the present specification, the melt index is measured at 190 ° C., 2.16 kg load condition according to ASTM D1238 under low density conditions of 0.875 g / cc to 0.895 g / cc, 0.1 g / 10 minutes to 10 g / 10 minutes and specifically 0.3 g/10 min to 9 g/10 min, more specifically 0.4 g/10 min to 7 g/10 min.
[35]
Meanwhile, the density may be 0.875 g/cc to 0.895 g/cc, specifically 0.876 g/cc to 0.892 g/cc, and more specifically 0.878 g/cc to 0.891 g/cc.
[36]
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 containing a transition metal compound having a characteristic structure, and a large amount of comonomer can be introduced. can have
[37]
In addition, the olefin-based polymer is (3) 0.5 J/g≤dH(100)≤3.0 J/g when measured by differential scanning calorimetry (SSA), and 1.0 J/g≤dH(90)≤6.0 ​​J/g It satisfies the requirement, specifically 0.9 J/g≤dH(100)≤2.0 J/g, and 1.5 J/g≤dH(90)≤5.0 J/g, more specifically 0.95 J /g≤dH(100)≤1.9 J/g, and 1.6 J/g≤dH(90)≤4.5 J/g can be satisfied.
[38]
In addition, the olefin-based polymer satisfies the requirements of (4) 15≤T(90)-T(50)≤30 and 50℃≤T(50)≤75℃ when measured by differential scanning calorimetry (SSA), , specifically, 16≤T(90)-T(50)≤25, and 52℃≤T(50)≤74℃, more specifically 17≤T(90)-T(50)≤ 25, and 54°C≤T(50)≤73°C may be satisfied.
[39]
In addition, the olefin-based polymer satisfies (5) the requirement that the melting point (Tm) measured by differential scanning calorimetry (DSC) is 55℃≤Tm≤80℃, specifically 60℃≤Tm≤80℃ and, more specifically, the requirement of 65°C≤Tm≤75°C may be satisfied.
[40]
In addition, the olefin-based polymer may additionally satisfy the requirement that (6) the glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) is -70°C≤Tg≤-43°C, and specifically, the glass transition temperature ( Tg) may be -60°C≤Tg≤-43°C, more specifically -51°C≤Tg≤-43°C.
[41]
In general, the melting temperature (Tm) using a differential scanning calorimeter (DSC) is heated at a constant rate to a temperature approximately 30°C higher than the melting temperature (Tm), and then the temperature is approximately 30°C lower than the glass transition temperature (Tg). After the first cycle of cooling at a constant rate to The differential scanning calorimeter precision measurement (SSA) measurement is performed by heating and cooling to a temperature just before the peak of the melting temperature (Tm) after the first cycle using a differential scanning calorimeter (DSC). This is a method to obtain more precise crystal information by repeatedly performing heating and cooling processes (Eur. Polym. J. 2015, 65, 132).
[42]
When a small amount of highly crystalline region is introduced into the olefinic polymer, it does not appear when measuring the melting temperature using a general differential scanning calorimeter (DSC), and the high-temperature melting peak can be measured through the differential scanning calorimeter precision measurement (SSA).
[43]
In addition, the olefin-based polymer according to an example of the present invention may further satisfy the requirement of (7) a weight average molecular weight (Mw) of 10,000 g/mol to 500,000 g/mol, and specifically, the weight average molecular weight (Mw) is 30,000 g/mol to 300,000 g/mol, more specifically 50,000 g/mol to 200,000 g/mol. In the present invention, the weight average molecular weight (Mw) is a polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC).
[44]
In addition, the olefin-based polymer according to an example of the present invention additionally 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 0.1 to 6.0 The phosphorus requirement may be satisfied, and the molecular weight distribution (MWD) may be specifically 1.0 to 4.0, more specifically 2.0 to 3.0.
[45]
In addition, the olefin-based polymer according to an example of the present invention additionally meets the requirement of (9) melt flow rate ratio (MFRR) of 5 to 10, which is the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). may be satisfied, and the melt flow rate ratio may be specifically 6 to 9, and more specifically 6 to 8.
[46]
The melt flow rate ratio (MFRR) means the ratio obtained by dividing MI 10 (melt index under a load of 10 kg and 190 ° C.) by MI 2.16 (melt index under a load of 2.16 kg and 190 ° C.) of the long side chain (LCB) of the polymer As the number decreases, the MFRR may exhibit a low value, and mechanical properties of the polymer may be improved.
[47]
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 styrenic monomer, or 2 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 a copolymer of an alpha-olefin having 3 to 10 carbon atoms.
[48]
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.
[49]
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-butene.
[50]
When the olefinic polymer is a copolymer of ethylene and alpha-olefin, the amount of the alpha-olefin is 90% by weight or less, more specifically 70% by weight or less, and even more specifically 5 to 60% by weight based on the total weight of the copolymer. It may be % by weight, and more specifically, may be 10% by weight to 50% by weight. When the alpha-olefin is included in the above range, the above-described physical properties may be appropriately implemented.
[51]
The olefin-based polymer according to an embodiment of the present invention having the above physical properties and structural characteristics, hydrogen gas is introduced in the presence of a metallocene catalyst composition including one or more transition metal compounds in a single reactor, and the olefin-based polymer It can be prepared through a continuous solution polymerization reaction that polymerizes the monomers. 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. may be, and more specifically, may be a random copolymer.
[52]
Specifically, the olefin-based copolymer of the present invention is a manufacturing method comprising the step of polymerizing an olefin-based monomer by introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of Formula 1, such as the following Hydrogen is added in the presence of a catalyst composition for olefin polymerization containing the transition metal compound of Formula 1, and it can be prepared by a continuous solution polymerization reaction using a continuous stirred tank reactor.
[53]
However, in the preparation of the olefin-based polymer according to an embodiment of the present invention, the scope of the structure of the transition metal compound of Formula 1 is not limited to a specific disclosed form, and all changes included in the spirit and technical scope of the present invention; It is to be understood as including equivalents and substitutes.
[54]
[Formula 1]
[55]

[56]
In Formula 1,
[57]
R 1 is the same as or different from each other, and each independently represents 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 metalloid 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;
[58]
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;
[59]
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;
[60]
M is a Group 4 transition metal;
[61]
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; or aryl amido.
[62]
[63]
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,
[64]
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; At least two of R 6 may be connected to each other to form an aliphatic or aromatic ring;
[65]
The 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,
[66]
M may be a Group 4 transition metal.
[67]
[68]
The transition metal compound represented by Formula 1 has a metal site 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 ) The angle is kept 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
[69]
In an example of the present invention, the amount of the hydrogen gas input may be 0.00005 to 0.001 parts by weight, specifically 0.00008 to 0.0008 parts by weight, and more specifically 0.0001 to 0.0005 parts by weight based on 1 part by weight of the olefinic monomer added to the reaction system. can be negative In addition, in one example of the present invention, when the olefinic polymer is polymerized by continuous solution polymerization, the hydrogen gas is 16 to 35 cc/min, specifically 18 to 1 kg/h of the olefinic monomer introduced into the reaction system. to 31 cc/min, more specifically, may be added in an amount of 18 to 29 cc/min.
[70]
In addition, in another example of the present invention, when the olefin-based polymer is a copolymer of ethylene and alpha-olefin, the hydrogen gas is 0.00007 to 0.0008 parts by weight, specifically 0.0008 to 0.0007 parts by weight, based on 1 part by weight of ethylene, More specifically, it may be added in an amount of 0.0001 to 0.0004 parts by weight. In addition, in one example of the present invention, when the olefin-based polymer is a copolymer of ethylene and alpha-olefin, and is polymerized by continuous solution polymerization, the hydrogen gas is 22 to 1 kg/h of ethylene introduced into the reaction system. 46 cc/min, specifically 25 to 44 cc/min, more specifically 25 to 40 cc/min.
[71]
In addition, the amount of hydrogen gas introduced in the step of polymerizing the olefinic monomer may be 20 to 40 sccm, specifically 22 to 38 sccm, more specifically 22 to 35 sccm. The input amount of the hydrogen gas is an amount based on when ethylene is introduced into the reaction system in an amount of 0.87 kg/h. When the input amount of hydrogen gas satisfies the above range in the presence of the catalyst composition for olefin polymerization including the transition metal compound of Formula 1, an olefin-based polymer satisfying the physical property range requirements of the olefin-based polymer according to an example of the present invention is prepared can be
[72]
[73]
Each of the substituents defined in the present specification will be described in detail as follows.
[74]
As used herein, the term 'hydrocarbyl group' is, unless otherwise specified, the number of carbon atoms consisting of only 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 to 20.
[75]
As used herein, the term 'halogen' means fluorine, chlorine, bromine or iodine, unless otherwise specified.
[76]
The term 'alkyl' as used herein, unless otherwise specified, refers to a straight-chain or branched hydrocarbon residue.
[77]
As used herein, the term 'cycloalkyl' refers to cyclic alkyl including cyclopropyl and the like, unless otherwise specified.
[78]
As used herein, the term 'alkenyl' refers to a straight-chain or branched alkenyl group, unless otherwise noted.
[79]
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.
[80]
The term 'aryl' as used herein, unless otherwise specified, represents an aromatic group having 6 to 20 carbon atoms, specifically phenyl, naphthyl, anthryl, phenanthryl, chrysenyl, pyrenyl, anthracenyl, pyridyl, dimethyl anilinyl, anisolyl, and the like, but is not limited thereto.
[81]
The alkylaryl group means an aryl group substituted by the alkyl group.
[82]
The arylalkyl group means an alkyl group substituted by the aryl group.
[83]
The ring (or heterocyclic group) means a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 ring atoms and containing at least one hetero atom, 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.
[84]
The alkyl amino group refers to an amino group substituted by the alkyl group, and includes, but is not limited to, a dimethylamino group and a diethylamino group.
[85]
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, and the like, but is limited to these examples only. not.
[86]
In the present specification, silyl may be silyl unsubstituted or substituted with alkyl having 1 to 20 carbon atoms, for example, silyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl , triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris(trimethylsilyl)silyl, and the like, but are not limited thereto.
[87]
[88]
The compound of Formula 1 may be of Formula 1-1, but is not limited thereto.
[89]
[Formula 1-1]
[90]

[91]
In addition, it may be a compound having various structures within the range defined in Formula 1 above.
[92]
[93]
Since the transition metal compound of Formula 1 can introduce a large amount of alpha-olefin as well as low-density polyethylene due to the structural characteristics of the catalyst, it is possible to prepare a low-density polyolefin copolymer of 0.850 g/cc to 0.890 g/cc. .
[94]
The transition metal compound of Formula 1 may be prepared by the following method as an example.
[95]
[Scheme 1]
[96]

[97]
[98]
In Scheme 1, R 1 to R 3 , M, Q 1 and Q 2 are as defined in Formula 1 above.
[99]
Formula 1 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.
[100]
[101]
The transition metal compound of Formula 1 may be used as a catalyst for polymerization in the form of a composition further comprising at least one of the cocatalyst compounds represented by Formula 2, Formula 3, and Formula 4 in addition to the above.
[102]
[Formula 2]
[103]
-[Al(R 4 )-O] a -
[104]
[Formula 3]
[105]
A(R 4 ) 3
[106]
[Formula 4]
[107]
[LH] + [W(D) 4 ] - or [L] + [W(D) 4 ] -
[108]
In Formulas 2 to 4,
[109]
R 4 may be the same 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,
[110]
A is aluminum or boron,
[111]
D is each independently aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, wherein the substituent is halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms and at least one selected from the group consisting of aryloxy having 6 to 20 carbon atoms,
[112]
H is a hydrogen atom,
[113]
L is a neutral or cationic Lewis base,
[114]
W is a group 13 element,
[115]
a is an integer greater than or equal to 2;
[116]
Examples of the compound represented by Formula 2 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).
[117]
Examples of the compound represented by Formula 3 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 trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.
[118]
Examples of the compound represented by Formula 4 include triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, and 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 Propylammonium tetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammoniumtetra(p-trifluoromethylphenyl)aluminum, trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum , tributylammoniumtetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, diethylammoniumtetrapentatenttraphenylaluminum, triphenyl Phosphonium tetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, triphenylcarboniumtetra(p-trifluoromethylphenyl) ) boron or triphenylcarboniumtetrapentafluorophenylboron.
[119]
The catalyst composition, as a first method, 1) contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 2 or Formula 3 to obtain a mixture; and 2) adding the compound represented by Formula 4 to the mixture.
[120]
In addition, the catalyst composition may be prepared by contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 4 as a second method.
[121]
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 2 or Formula 3 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 to the compound represented by Formula 2 or Formula 3 exceeds 1/2, the amount of the alkylating agent is very small, and there is a problem that the alkylation of the metal compound cannot proceed completely, , 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 4, there is a problem in that the activation of the alkylated metal compound cannot be completed. . In addition, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 4 may be 1/25 to 1, specifically 1/10 to 1, and more specifically 1/5 to can be 1. When the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 4 exceeds 1, the amount of the activator is relatively small, so the activation of the metal compound is not completely achieved, and thus the activity of the catalyst composition may fall, and if the molar ratio is less than 1/25, the metal compound is fully activated, but the unit price of the catalyst composition may not be economical or the purity of the resulting polymer may be deteriorated with an excess of the remaining activator.
[122]
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 to the compound represented by Formula 4 may be 1/10,000 to 1/10, and specifically 1/5,000 It may be 1/100 to 1/100, and more specifically, it may be 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 generated 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 remaining excess activator.
[123]
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.
[124]
In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a supported form on a carrier.
[125]
The carrier may be used without 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.
[126]
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 olefin polymerization. As a result, it is possible to prevent the occurrence of fouling in which the reactor wall surface or polymer particles are agglomerated during the production 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.
[127]
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.
[128]
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 .
[129]
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.
[130]
The polymerization reaction of the olefin monomer may be performed under an inert solvent, and examples of the inert solvent include benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, but not limited thereto.
[131]
Polymerization of the olefin-based polymer may be made at a temperature of about 25 °C to about 500 °C, specifically 80 °C to 250 °C, more preferably at a temperature of 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
[132]
Since the olefin-based polymer of the present invention has improved physical properties, it is used for blow molding and extrusion in various fields and uses such as materials for automobiles, electric wires, toys, textiles, medical materials, etc. It is useful for molding or injection molding, and in particular, it can be usefully used for automobiles requiring excellent impact strength.
[133]
In addition, the olefin-based polymer of the present invention may be usefully used in the manufacture of a molded article.
[134]
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.
[135]
[136]
Example
[137]
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 several different forms and is not limited to the embodiments described herein.
[138]
[139]
Preparation Example 1: Preparation of transition metal compound
[140]

[141]
(1) Preparation of 2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline
[142]
(i) Preparation of lithium carbamate
[143]
2-methylindoline (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%.
[144]
(ii) Preparation of 2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline
[145]
[146]
The lithium carbamate compound (8.47 g, 42.60 mmol) prepared in step (i) was placed in a Schlenk flask. Then, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were sequentially added. The Schlenk flask was immersed in a low temperature bath at -20°C made with acetone and a small amount of dry ice and stirred for 30 minutes, and then t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of the reaction mixture changed to red. Stirring was continued for 6 hours while maintaining -20°C. CeCl 3 ·2LiCl solution (129 mL, 0.33 M, 42.60 mmol) dissolved in tetrahydrofuran and tetramethylcyclopentynone (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 the filtrate was transferred to a separatory funnel, hydrochloric acid (2 N, 80 mL) was added, 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 an oily phase. The yield was 19%.
[147]
1 H NMR(C 6 D 6 ): δ 6.97(d, J=7.2Hz, 1H, CH), δ 6.78(d, J=8Hz, 1H, CH), δ 6.67(t, J=7.4Hz, 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.
[148]
[149]
(2) [(2-Methylindolin-7-yl)tetramethylcyclopentadienyl-eta5,kappa-N]titanium dimethyl ([(2-Methylindolin-7-yl)tetramethylcyclopentadienyl-eta5,kapa-N] production of titanium dimethyl)
[150]
(i) Preparation of [(2-methylindolin-7-yl)tetramethylcyclopentadienyl- η 5 , κ -N]dilithium compound
[151]
2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-indoline (2.25 g, 8.88 mmol) prepared through step (1) in a dry box and After putting 50 mL of diethyl ether into a round flask, the temperature was lowered to -30°C, and n-BuLi (4.9 g, 2.5 M, 17.8 mmol) was slowly added while 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 salt compound coordinated with 0.58 equivalents of diethyl ether (1.37 g, 50 %).
[152]
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-CH 3 ) ppm.
[153]
[154]
(ii) (2-methylindolin-7-yl) tetramethylcyclopentadienyl- η 5 , κ -N] Preparation of titanium dimethyl
[155]
In a dry box, TiCl 4 ·DME (1.24 g, 4.44 mmol) and diethyl ether (50 mL) were placed in a round flask, and while stirring at -30°C, MeLi (6.1 mL, 8.88 mmol, 1.4 M) was slowly added thereto. After stirring for 15 minutes, the [(2-methylindolin-7-yl)tetramethylcyclopentadienyl- η 5 , κ -N]dilithium compound prepared in step (i) (1.37 g, 4.44 mmol) was placed in the flask. The mixture was stirred for 3 hours while raising the temperature to room temperature. After the reaction was completed, vacuum was applied to remove the solvent, dissolved in pentane, and filtered to obtain a filtrate. Vacuum was applied to remove pentane to give the title compound.
[156]
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
[157]
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.
[158]
[159]
Example 1
[160]
After the 1.5 L continuous process reactor was charged with hexane solvent (6 kg/h) and 1-butene (0.35 kg/h), the temperature at the top of the reactor was preheated to 143.5°C. Triisobutylaluminum compound (0.03 mmol/min), the transition metal compound (0.40 μmol/min) obtained in Preparation Example, and dimethylanilinium tetrakis(pentafluorophenyl) borate promoter (1.20 μmol/min) were simultaneously added was introduced into the reactor. Then, hydrogen gas (25 cc/min) and ethylene (0.87 kg/h) were introduced into the reactor and maintained at 143.5° C. for at least 30 minutes in a continuous process at a pressure of 89 bar to proceed with a copolymerization reaction to obtain a copolymer. . After drying in a vacuum oven for more than 12 hours, physical properties were measured.
[161]
[162]
Examples 2 to 6
[163]
The copolymerization reaction was carried out in the same manner as in Example 1, and the amount of transition metal compound, the amount of catalyst and co-catalyst, and the reaction temperature, hydrogen input, and amount of comonomer were respectively changed as shown in Table 1 below to proceed with the copolymerization reaction. synthesis was obtained.
[164]
[165]
Comparative Example 1
[166]
DF840 from Mitsui Chemicals was purchased and used.
[167]
[168]
Comparative Example 2
[169]
DF810 from Mitsui Chemicals was purchased and used.
[170]
[171]
[Table 1]
Catalyst usage
(μmol
/min) Cocatalyst
(μmol
/min) TiBAl
(mmol
/min) Ethylene
(kg/h) Hexane
(Kg/h) 1-Butene
(kg/h) Hydrogen
(cc/min) Reaction temperature
(℃)
Example 1 0.40 1.20 0.03 0.87 7 0.35 25 143.5
Example 2 0.20 0.60 0.03 0.87 7 0.35 31 139.0
Example 3 0.36 1.08 0.03 0.87 7 0.23 28 138.6
Example 4 0.30 0.90 0.03 0.87 7 0.23 28 138.6
Example 5 0.29 0.87 0.03 0.87 7 0.29 33 140.2
Example 6 0.32 0.96 0.03 0.87 7 0.23 28 139.9
[172]
Experimental example
[173]
The copolymers of Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated for physical properties according to the following method, and are shown in Table 2 below.
[174]
1) Density of polymer
[175]
Measured by ASTM D-792.
[176]
2) Polymer Melt Index (MI)
[177]
It was measured by ASTM D-1238 (Condition E, 190°C, 2.16 kg load).
[178]
3) Melt flow rate ratio (MFRR)
[179]
Measure MI10 and MI2.16 according to ASTM D-1238 [Condition E, MI10 (190℃, 10kg load), MI2.16(190℃, 2.16kg load)], and then divide MI10 by MI2.16 to melt flow rate The ratio (MFRR) was calculated.
[180]
4) Weight average molecular weight (Mw, g/mol) and molecular weight distribution (MWD)
[181]
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.
[182]
- Column: PL Olexis
[183]
- Solvent: TCB (Trichlorobenzene)
[184]
- Flow rate: 1.0 ml/min
[185]
- Sample concentration: 1.0 mg/ml
[186]
- Injection volume: 200 μl
[187]
- Column temperature: 160℃
[188]
- Detector: Agilent High Temperature RI detector
[189]
- Standard: Polystyrene (corrected by cubic function)
[190]
5) Melting point (Tm) and glass transition temperature (Tg)
[191]
It was obtained using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 250) manufactured by TA Instruments. That is, after increasing the temperature to 150° C., maintaining it at that temperature for 1 minute, then lowering it to -100° C., and increasing the temperature again to observe the DSC curve.
[192]
6) T(90), T(50) dH(100), and dH(90)
[193]
The differential scanning calorimeter (DSC: Differential Scanning Calorimeter 250) manufactured by TA Instruments was obtained by SSA (Successive self-nucleation/annealing) measurement method.
[194]
Specifically, in the first cycle, the temperature was increased to 150°C, held at that temperature for 1 minute, and then cooled to -100°C. In the second cycle, the temperature was increased to 120 °C, held at that temperature for 30 minutes and then cooled to -100 °C. In the third cycle, the temperature was increased to 110 °C, held at that temperature for 30 minutes and then cooled to -100 °C. In this way, the process of raising the temperature at 10°C intervals and cooling to -100°C was repeated until -60°C so that crystallization was performed for each temperature section. At this time, the rate of rise and fall of the temperature was controlled at 10 °C/min, respectively.
[195]
In the last cycle, the heat capacity was specified while increasing the temperature to 150°C.
[196]
The temperature-heat capacity curve obtained in this way was integrated for each section to fractionate the heat capacity of each section compared to the total heat capacity. Here, the temperature at which 50% of the total heat capacity is melted is defined as T(50), and the temperature at which 90% of the total heat capacity is melted is defined as T(90).
[197]
In addition, when measuring SSA, the sum of the enthalpy of melting (ΔH) at 90°C or higher was defined as dH(90), and the sum of the melting enthalpy (ΔH) at 100°C or higher was added to define the sum as dH(100). .
[198]
Fig. 1 shows a graph of T (50) versus the density of the polymers of Examples 1 to 6 and the polymers of Comparative Examples 1 and 2, and in Fig. 2, differential scanning calorimetry precision for the polymers of Examples 5 and 2 A graph is shown as a result of measurement by the measuring method (SSA).
[199]
7) Tensile strength and elongation of polymer
[200]
The olefinic copolymers of Example 5 and Comparative Example 2 were each extruded to prepare pellets, and then tensile strength and elongation at break were measured according to ASTM D638 (50 mm/min).
[201]
8) flexural modulus
[202]
Measurements were made according to ASTM D790 using an INSTRON 3365 instrument.
[203]
9) Hardness (shore A)
[204]
Hardness was measured according to ASTM D2240 standard using TECLOCK's GC610 STAND for Durometer and Mitutoyo's Shore Durometer Type A.
[205]
[206]
[Table 2]
Density
(g/mL) MI
(g/
10min) MFRR Tg Mw
(g/mol) MWD SSA
(℃) Tm
(℃) T(50) T(90) T(90)-T(50) dH(100)
(J/g) dH(90)
(J/g)
Example 1 0.8788 1.95 7.1 -500.8 94021 2.17 61.7 55.2 80.1 24.9 0.96 1.62
Example 2 0.8880 3.21 6.48 -44.8 86057 2.10 71.1 68.1 90.1 22.0 1.82 4.25
Example 3 0.8830 1.61 7.01 -47.3 98857 2.16 67.4 61.5 84.8 23.3 1.28 2.29
Example 4 0.8860 1.69 6.62 -44.9 100370 1.96 70.4 66.2 88.4 22.2 1.35 2.64
Example 5 0.8850 1.16 6.53 -43.1 108628 2.03 70.6 66.9 84.4 17.5 0.98 1.63
Example 6 0.8900 0.72 7.46 -43.1 117140 1.98 74.4 71.6 90.2 18.6 1.26 2.39
Comparative Example 1 0.8840 3.44 6.31 -42.9 83425 1.93 70.9 56.0 76.7 20.7 0 0
Comparative Example 2 0.8840 1.18 6.51 -43.3 114216 1.90 69.3 58.1 77.8 19.7 0 0
[207]
[Table 3]
Density
(g/mL) MI
(g/10min) Tensile strength
(Mpa) Flexural modulus
(Mpa) Elongation
(%) Hardness
(Shore A)
Example 2 0.888 3.21 18.1 34.26 >700 92.9
Comparative Example 1 0.884 3.44 15.0 27.91 >700 85.3
Example 5 0.885 1.16 26.8 36.98 >700 88.2
Comparative Example 2 0.884 1.18 25.1 30.37 >700 85.8
[208]
When comparing Examples and Comparative Examples having the same level of density and MI in Table 2, Examples 2 and 5 exhibited smaller T(90)-T(50) values ​​compared to Comparative Examples 1 and 2. In particular, the olefinic polymers of Examples 2 and 5 satisfy the requirements of 0.5 J/g≤dH(100)≤3.0 J/g and 1.0 J/g≤dH(90)≤6.0 ​​J/g, but in Comparative Example In the olefin-based polymer of 2, both dH(100) and dH(90) showed a value of 0, which was not satisfied. Through Table 3, the mechanical strength of Example 5 and Comparative Example 2 having an equivalent level of density and MI can be compared. In Examples 2 and 5, it can be seen that the polymer crystal region melted at a high temperature was introduced to increase the mechanical rigidity, so that the tensile strength, flexural modulus, and hardness were increased compared to Comparative Example 2.
[209]
On the other hand, FIG. 1 shows a graph of T (50) for the density of the olefin-based polymer of Examples 1 to 6 and the olefin-based polymer of Comparative Examples 1 and 2, and FIG. 2 shows the graphs of Examples 5 and 2 A graph is shown of the results measured by differential scanning calorimetry precision (SSA) for the polymer.
[210]
Referring to FIG. 1 , in the olefin-based polymers of Examples 1 to 6, T(50) increases as the density increases, and it can be confirmed that the density and T(50) exhibit a linear correlation. On the other hand, the olefin-based polymers of Comparative Examples 1 and 2 did not show a particular correlation between the density and T(50). On the other hand, referring to FIG. 2 , it can be seen that the olefin-based polymer of Example 5 is eluted at a higher overall temperature than the olefin-based polymer of Comparative Example 5. Through this, it can be confirmed that the olefin-based polymer of Example 5 has a high crystallinity region introduced, and the polymer of Example 5 can exhibit high tensile strength and hardness due to the introduction of the high crystallinity region.
[211]
As such, the olefinic polymers of Examples 1 to 6 are polymers obtained by polymerizing an olefinic monomer by introducing hydrogen gas, and 0.5 J/g≤dH(100)≤3.0 J when measured by differential scanning calorimetry (SSA). /g, and satisfies 1.0 J/g≤dH(90)≤6.0 ​​J/g, and exhibits high mechanical rigidity.
Claims
[Claim 1]
Olefin-based polymers satisfying the following requirements (1) to (5): (1) Melt index (MI, 190°C, load condition of 2.16 kg): 0.1 to 10.0 g/10 min; (2) density (d): 0.875 to 0.895 g/cc; (3) 0.5 J/g≤dH(100)≤3.0 J/g, and 1.0 J/g≤dH(90)≤6.0 ​​J/g when measured by differential scanning calorimetry (SSA); (4) 15≤T(90)-T(50)≤30 in differential scanning calorimetry precision measurement (SSA), and 50°C≤T(50)≤75°C; (5) a melting point (Tm) measured by differential scanning calorimetry (DSC) of 55°C≤Tm≤80°C; Here, T(50) and T(90) are, respectively, in the differential scanning calorimeter precision measurement (SSA) measurement result, when the heat capacity of each section is fractionated compared to the total heat capacity by integrating the temperature-heat capacity curve for each section, compared to the total heat capacity 50% and 90% are the melting temperatures, respectively, dH(90) is the sum of melting enthalpies at 90°C or higher, and dH(100) is the sum of melting enthalpies at 100°C or higher.
[Claim 2]
The olefin according to claim 1, wherein the olefin-based polymer further satisfies (6) a glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) of -70°C≤T(50)≤-43°C. based polymer.
[Claim 3]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer further satisfies (7) a weight average molecular weight (Mw) of 10,000 g/mol to 500,000 g/mol.
[Claim 4]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer further satisfies the requirement of (8) a molecular weight distribution (MWD) of 0.1 to 6.0.
[Claim 5]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer further satisfies the requirement of (9) a melt flow rate ratio (MFRR) of 5 to 10.
[Claim 6]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer has a melt index (MI) of 0.3 g/10 min to 9 g/10 min.
[Claim 7]
The olefinic polymer according to claim 1, wherein T(90)-T(50) is 16≤T(90)-T(50)≤25, and 52°C≤T(50)≤74°C. .
[Claim 8]
The olefin-based polymer according to claim 1, wherein dH(100) and dH(90) satisfy the requirements of 0.9≤dH(100)≤2.0 and 1.5≤dH(90)≤5.0.
[Claim 9]
The olefin-based polymer according to claim 1, wherein the melting point (Tm) satisfies the requirement of 60°C≤Tm≤80°C.
[Claim 10]
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 11]
11. The method of claim 10, 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 Sene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4 -Butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene, including any one or a mixture of two or more selected from the group consisting of olefins based polymer.
[Claim 12]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer is a copolymer of ethylene and 1-butene.
[Claim 13]
According to claim 1, wherein the olefin-based polymer is obtained by a manufacturing method comprising the step of polymerizing the olefin-based monomer by introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of formula (1) Olefin-based polymer: [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, alkenyl having 2 to 20 carbon atoms, aryl, silyl, alkylaryl , arylalkyl, or a metalloid radical of a Group 4 metal substituted with hydrocarbyl, wherein the two R 1 are linked 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; 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 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; or aryl amido.
[Claim 14]
The olefin-based polymer according to claim 13, wherein the amount of hydrogen gas is 20 to 40 sccm.
[Claim 15]
The olefin-based polymer according to claim 13, wherein the olefin-based polymer is prepared by a continuous solution polymerization reaction using a continuous stirred tank reactor by adding hydrogen in the presence of the catalyst composition for olefin polymerization.