Specification
Title of Invention: Olefin Polymer
Technical field
[One]
[Mutual citation with related application]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0179656 filed on December 26, 2017, and all contents disclosed in the documents of the Korean patent application are incorporated as part of this specification.
[3]
[Technical field]
[4]
The present invention relates to an olefin-based polymer, and more specifically, to a low-density olefin-based polymer that exhibits excellent anti-blocking properties prepared using two types of transition metal compound catalysts.
Background
[5]
Polyolefins have excellent moldability, heat resistance, mechanical properties, hygiene quality, water vapor permeability, and appearance properties of molded products, and are widely used for extrusion molded products, blow molded products and injection molded products. However, since polyolefins, especially polyethylene, do not have a polar group in their molecule, they have low compatibility with polar resins such as nylon, and low adhesiveness with polar resins and metals. As a result, it has been difficult to blend polyolefins with polar resins or metals or to laminate them with these materials. Further, the molded article of polyolefin has a problem of low surface hydrophilicity and antistatic property.
[6]
In order to solve this problem and increase the affinity for polar materials, a method of grafting a polar group-containing monomer onto a polyolefin through radical polymerization has been widely used. However, this method has a problem of low miscibility due to poor viscosity balance between the graft polymer and polar resin due to intramolecular crosslinking and cleavage of the molecular chain of the polyolefin during the graft reaction. In addition, there was a problem in that the appearance characteristics of the molded article were low due to a gel component generated by intramolecular crosslinking or a foreign substance generated by cleavage of a molecular chain.
[7]
In addition, as a method of preparing 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 a polar monomer is copolymerized using a 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 made 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 metallocene compound having a ligand of a non-crosslinked cyclopentadienyl group, a crosslinked or non-crosslinked bisindenyl group, or an ethylene bridged unsubstituted indenyl group/fluorenyl group is used as a catalyst to prepare a polyolefin containing a polar group. As a method, a method of using a metallocene catalyst is also known. However, these methods have a disadvantage of very low polymerization activity. For this reason, although a method of protecting a polar group by a protecting group is being carried out, when introducing a protecting group, there is a problem that the process becomes complicated because the protecting group must be removed again after the reaction.
[10]
Ansa-metallocene compound is an organometallic compound comprising 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 The structure is determined.
[11]
Such ansa-metallocene compounds are used as catalysts in the production of olefin-based homopolymers or copolymers. In particular, it is known that an ansa-metallocene compound containing a cyclopentadienyl-fluorenyl ligand can produce a high molecular weight polyethylene, through which the microstructure of polypropylene can be controlled. have.
[12]
In addition, an ansa-metallocene compound containing an indenyl ligand is known to be capable of producing a polyolefin having excellent activity and improved stereoregularity.
[13]
As such, various studies have been made on ansa-metallocene compounds that can control the microstructure of olefin-based polymers while having higher activity, but the degree is still insufficient.
Detailed description of the invention
Technical challenge
[14]
An object to be solved of the present invention is to provide a low-density olefin-based polymer that exhibits excellent anti-blocking properties prepared using two kinds of transition metal compound catalysts.
Means of solving the task
[15]
In order to solve the above problems, the present invention has a (1) density (d) of 0.850 g/cc to 0.865 g/cc, and (2) a melt index (Melt Index, MI, 190°C, 2.16 kg load condition) of 0.1 g/10min to 3.0g/10min, (3) soluble fraction (SF, Soluble Fraction) at -20°C on cross-fractionation chromatography (CFC) is 8% by weight or more, and the corresponding fraction It provides an olefin-based polymer having a weight average molecular weight (Mw) of 50,000 g/mol to 500,000 g/mol.
Effects of the Invention
[16]
The olefin-based polymer according to the present invention is a low-density olefin-based polymer and exhibits improved anti-blocking properties by controlling the molecular weight of the ultra-low crystalline region.
Best mode for carrying out the invention
[17]
Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.
[18]
The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of ​​the present invention based on the principle that there is.
[19]
In the present specification, 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". In addition, the "interpolymer" refers to a polymer prepared by polymerization of two or more different types of monomers. The generic term "interpolymer" refers not only to the term "copolymer" (usually used to refer to polymers made from two different monomers), as well as to polymers (made from three different types of monomers) As used) the term "terpolymer". This includes polymers made by polymerization of four or more types of monomers.
[20]
[21]
The olefin polymer according to the present invention satisfies the requirements of the following (1) to (3).
[22]
(1) Density (d) is 0.850 g/cc to 0.865 g/cc, and (2) Melt Index (MI, 190° C., 2.16 kg load condition) is 0.1 g/10 min to 3.0 g/10 min. And (3) the soluble fraction (SF, Soluble Fraction) at -20°C on cross-fractionation chromatography (CFC) is 8% by weight or more, and the weight average molecular weight (Mw) of the fraction is 50,000 g /mol to 500,000 g/mol.
[23]
When measuring the cross-fractionation chromatography (CFC), the fraction eluted at a lower temperature has lower crystallinity, and in this specification, at -20°C or less on the cross-fractionation chromatography (CFC) The eluted soluble fraction (SF, Soluble Fraction) is defined as an ultra-low crystalline region.
[24]
In general, as the density of the polymer decreases, the crystallinity decreases, the ultra-low crystallinity region increases, and the impact strength improves. However, it is difficult to prepare an ultra-low crystalline region above a certain level in a conventional olefin-based polymer, and when prepared, the molecular weight of the region decreases, resulting in deterioration of anti-blocking properties. The olefin-based polymer according to the present invention can exhibit excellent anti-blocking properties by maintaining a high molecular weight of the region while maintaining a high ultra-low crystalline content at the same density as compared to a conventional olefin-based polymer.
[25]
The olefin-based polymer according to the present invention may exhibit a density of 0.850 g/cc to 0.865 g/cc, and specifically 0.853 g/cc to 0.863 g/cc, as measured according to ASTM D-792.
[26]
The melt index (MI) can be adjusted by adjusting the amount of the catalyst used in the polymerization of the olefin-based polymer to the comonomer, and affects the mechanical properties, 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 in a low density condition of 0.850 g/cc to 0.865 g/cc, and may be 0.1 g/10 min to 3 g/10 min. And, specifically, 0.2 g/10 minutes to 2 g/10 minutes, more specifically 0.25 g/10 minutes to 1.8 g/10 minutes.
[27]
The olefin-based polymer according to the present invention has a soluble fraction (SF, Soluble Fraction) at -20°C on cross-fractionation chromatography (CFC, Cross-fractionation Chromatography) of 8 wt% or more, specifically 10 wt% to 50 wt% And, the weight average molecular weight (Mw) of the fraction can be maintained at least 50,000. The olefin-based polymer according to an example of the present invention has a high ultra-low crystalline content because the soluble fraction at -20°C satisfies the above range on cross-fraction chromatography, and by maintaining a high molecular weight of the fraction, it has more excellent anti-blocking properties. Can be demonstrated.
[28]
In addition, the olefin-based polymer according to an exemplary embodiment of the present invention has a weight average molecular weight (Mw) of the soluble fraction at -20°C on the cross-fraction chromatography defined as an ultra-low crystalline region, specifically 50,000 g/mol to 500,000 g/ mol may be satisfied, more specifically 50,000 g/mol to 300,000 g/mol, and even more specifically 60,000 g/mol to 200,000 g/mol. The olefin-based polymer according to an exemplary embodiment of the present invention exhibits a high high molecular weight ultra-low crystal content, since the soluble fraction at -20°C on cross-fraction chromatography satisfies the weight average molecular weight (Mw) range, and in particular, the density (1) And while satisfying the melt index (2), the content of the soluble fraction and the weight average molecular weight (Mw) of the soluble fraction are satisfied. It shows the fraction content and the weight average molecular weight of the soluble fraction, and accordingly, excellent anti-blocking properties can be exhibited.
[29]
In addition, the olefin-based polymer according to an exemplary embodiment of the present invention is a low-density polymer exhibiting the above density range and has a high ultra-low crystalline content, so that the CFC elution end temperature may be 60°C or less, specifically 20°C to 60°C, more specifically It may be 20 ℃ to 55 ℃, more specifically 25 ℃ to 45 ℃. The olefin-based polymer of the present invention has an elution end temperature of 60° C. or less, which has low overall crystallinity, and thus has excellent impact strength. In particular, it is completely distinguished from LDPE, HDPE, LLDPE, etc., which have fractions that elute even after 60°C.
[30]
In addition, the olefin-based polymer according to an example of the present invention has a weight average molecular weight (Mw) and a number average molecular weight (Mn) ratio (Mw/Mn) of (4) molecular weight distribution (MWD; Molecular Weight Distribution) of 1.0 to 3.0, Specifically, it may be 1.5 to 2.8, more specifically 1.8 to 2.6. The olefin-based polymer according to an exemplary embodiment of the present invention may exhibit a narrow molecular weight distribution by being polymerized using a catalyst composition including two types of transition metal compounds having a characteristic structure.
[31]
In general, the density of the olefin-based polymer is affected by the type and content of the monomers used in polymerization, the degree of polymerization, and the like, and in the case of a copolymer, the content of the comonomer is greatly influenced. The olefin-based polymer of the present invention is polymerized using a catalyst composition containing two types of transition metal compounds having a characteristic structure, and a large amount of comonomer can be introduced. It has a low density of, and as a result, it can exhibit excellent foaming processability.
[32]
The olefin-based polymer has (5) a weight average molecular weight (Mw) of 10,000 g/mol to 500,000 g/mol, specifically 30,000 g/mol to 300,000 g/mol, and more specifically 50,000 g/mol within the above molecular weight distribution range. mol to 200,000 g/mol. In the present invention, the weight average molecular weight (Mw) is a molecular weight in terms of polystyrene analyzed by gel permeation chromatography (GPC).
[33]
The olefin-based polymer may have a melting temperature (Tm) obtained from a DSC curve obtained by measuring with a differential scanning calorimeter (DSC) of 100°C or less, specifically 80°C or less, and more specifically 10°C to 60°C.
[34]
Further, the olefin-based polymer according to the exemplary embodiment of the present invention, (4) a molecular weight distribution (MWD, density molecular weight) is from 1.0 to 3.0, (6) MI 10 / MI 2. 16 > 7.91 (MI 2.16 ) -0.188 the intended I can. The MI 10 and MI 2. 16 represent a melt index (MI), measured by ASTM D-1238, and may be used as a label for molecular weight.
[35]
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 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 3 to 10 carbon atoms.
[36]
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-itocene, norbornene, nobonadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1,5 -Pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and a mixture of two or more selected from the group consisting of 3-chloromethylstyrene.
[37]
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.
[38]
When the olefin-based polymer is a copolymer of ethylene and an 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. % By weight, and even more specifically, may be 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.
[39]
The olefin-based polymer according to an embodiment of the present invention having the above physical properties and constitutional characteristics is prepared through a continuous solution polymerization reaction in the presence of a metallocene catalyst composition containing at least one transition metal compound in a single reactor. Can be. Accordingly, in the olefin-based polymer according to an embodiment of the present invention, a block composed of two or more repeating units derived from any one of the monomers constituting the polymer in the polymer is connected in a linear manner is not formed. 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. It may be, and more specifically, may be a random copolymer.
[40]
Specifically, the olefin-based copolymer of the present invention comprises a transition metal compound of Formula 1 and a transition metal compound of Formula 2 in an equivalent ratio of 1:1 to 1:5, specifically 1:1 to 1:4 In the presence of a catalyst composition for olefin polymerization, it can be obtained by a production method comprising the step of polymerizing an olefin-based monomer.
[41]
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 the spirit and technical scope of the present invention It is to be understood to include all included modifications, equivalents or substitutes.
[42]
[Formula 1]
[43]

[44]
In Formula 1,
[45]
R 1 is the same as or different from each other, and each independently hydrogen, a C 1 to C 20 alkyl, a C 2 to C 20 alkenyl, aryl, silyl, alkyl aryl, arylalkyl, or a metal of a Group 4 metal substituted with hydrocarbyl A Lloyd radical, wherein the two R 1 may be 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;
[46]
R 2 are the same as or different from each other, and each independently hydrogen; halogen; Alkyl of 1 to 20 carbon atoms; Aryl; Alkoxy; Aryloxy; An amido radical, and two or more of R 2 may be linked to each other to form an aliphatic ring or an aromatic ring;
[47]
R 3 is the same as or different from each other, and each independently hydrogen; halogen; Alkyl of 1 to 20 carbon atoms; Or a nitrogen-containing aliphatic or aromatic ring substituted or unsubstituted with an aryl radical, and when the number of the substituents is plural, two or more substituents among the substituents may be linked to each other to form an aliphatic or aromatic ring;
[48]
M 1 is a Group 4 transition metal;
[49]
Q 1 and Q 2 are each independently halogen; Alkyl of 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;
[50]
[Formula 2]
[51]

[52]
In Chemical Formula 2,
[53]
R 4 is the same as or different from each other, and each independently hydrogen, a C 1 to C 20 alkyl, a C 2 to C 20 alkenyl, aryl, silyl, alkylaryl, arylalkyl, or a metal of a Group 4 metal substituted with hydrocarbyl It is a Lloyd group, and the two R 1 may be linked to each other by an alkylidine containing an alkyl having 1 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms to form a ring;
[54]
R 5 are the same as or different from each other, and each independently hydrogen; halogen; Alkyl of 1 to 20 carbon atoms; Aryl; Alkoxy; Aryloxy; Amido, and two or more of R 2 may be connected to each other to form an aliphatic ring or an aromatic ring;
[55]
R 6 are the same as or different from each other, and each independently hydrogen; halogen; Alkyl of 1 to 20 carbon atoms; Or an aryl-substituted or unsubstituted, nitrogen-containing aliphatic or aromatic ring, and when the number of substituents is plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;
[56]
M 2 is a Group 4 transition metal;
[57]
Q 3 and Q 4 are each independently halogen; Alkyl of 1 to 20 carbon atoms; Alkenyl; Aryl; Alkylaryl; Arylalkyl; Alkyl amido having 1 to 20 carbon atoms; Aryl amido; Or alkylidene having 1 to 20 carbon atoms.
[58]
[59]
Further, 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 of 1 to 20 carbon atoms; Aryl; Or it may be silyl,
[60]
R 3 is 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 may be amido; Two or more adjacent R 3 of R 3 may be linked to each other to form an aliphatic or aromatic ring;
[61]
Q 1 and Q 2 are the same as or different from each other, and each independently halogen; Alkyl of 1 to 20 carbon atoms; Alkylamidos having 1 to 20 carbon atoms; May be an arylamido,
[62]
M 1 may be a Group 4 transition metal.
[63]
In addition, in Formula 2, R 4 and R 5 are the same as or different from each other, and each independently hydrogen; Alkyl of 1 to 20 carbon atoms; Aryl; Or it may be silyl,
[64]
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 may be amido; Wherein R 6 in at least two R 6 are connected to each other can form a aliphatic or aromatic ring;
[65]
Q 3 and Q 4 are the same as or different from each other, and each independently halogen; Alkyl of 1 to 20 carbon atoms; Alkylamidos having 1 to 20 carbon atoms; May be an arylamido,
[66]
M 2 may be a Group 4 transition metal.
[67]
[68]
In addition, the transition metal compound represented by Chemical Formula 1 or Chemical Formula 2 has a narrow Cp-MN angle structurally, and Q 1 − The MQ 2 (Q 3 -MQ 4 ) angle is characterized by keeping it wide. In addition, Cp, tetrahydroquinoline, nitrogen and metal sites are sequentially connected by a cyclic bond to form a more stable and rigid pentagonal ring structure. Therefore, when these compounds are activated by reacting with a cocatalyst such as methylaluminoxane or B(C 6 F 5 ) 3 and then applied to olefin polymerization, the characteristics of high activity, high molecular weight and high co-polymerization even at high polymerization temperatures are achieved. It is possible to polymerize the possessed olefin-based polymer.
[69]
Each of the substituents defined in the present specification will be described in detail as follows.
[70]
The term'hydrocarbyl group' as used herein, unless otherwise noted, is a carbon number consisting of carbon and hydrogen regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl or arylalkyl. It means a 1-20 monovalent hydrocarbon group.
[71]
The term'halogen' as used herein means fluorine, chlorine, bromine or iodine unless otherwise stated.
[72]
The term'alkyl' as used herein, unless otherwise stated, means a straight or branched chain hydrocarbon moiety.
[73]
The term “alkenyl” as used herein refers to a linear or branched alkenyl group unless otherwise stated.
[74]
The branched chain is alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl of 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.
[75]
According to an example of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but are not limited thereto.
[76]
The alkylaryl group means an aryl group substituted by the alkyl group.
[77]
The arylalkyl group refers to an alkyl group substituted by the aryl group.
[78]
The ring (or heterocyclic group) refers to a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 ring atoms and including 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 or may not be substituted with an alkyl group. Examples of these include indoline, tetrahydroquinoline, and the like, but the present invention is not limited thereto.
[79]
The alkyl amino group refers to an amino group substituted by the alkyl group, and includes a dimethylamino group and a diethylamino group, but are not limited thereto.
[80]
According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but are limited to these examples. no.
[81]
The compound of Formula 1 may be at least one selected from the group consisting of the following 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 Formula 2-1, but is not limited thereto. Does not.
[82]
[Formula 1-1]
[83]

[84]
[Formula 1-2]
[85]

[86]
[Formula 2-1]
[87]

[88]
In addition, it may be a compound having various structures within the range defined in Formulas 1 and 2.
[89]
[90]
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, since a large amount of alpha-olefin as well as low-density polyethylene can be introduced due to the structural characteristics of the catalyst. It is possible to prepare a low density polyolefin copolymer. 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 It has, and it is possible to prepare an olefin-based polymer having a low density.
[91]
[92]
The transition metal compounds of Formulas 1 and 2 may be prepared by the following method as an example.
[93]
[Scheme 1]
[94]

[95]
In Reaction Scheme 1, R 1 to R 3 , M 1 , Q 1 , and Q 2 are as defined in Formula 1, respectively.
[96]
In addition, the transition metal compound of Formula 2 may be prepared by the following method as an example.
[97]
[Scheme 2]
[98]

[99]
In Scheme 2, R 4 to R 6 , M 2 , Q 3 , and Q 4 are as defined in Chemical Formula 2.
[100]
Formula 1 and Formula 2 may be prepared according to the method described in Patent Publication No. 2007-0003071, the contents of the patent document are all included in the present specification.
[101]
The transition metal compound of Formula 1 and the transition metal compound of Formula 2 are mixed alone or in a group represented by the following Formulas 3, 4, and 5 in addition to the transition metal compound of Formula 1 and the transition metal compound of Formula 2 In the form of a composition further comprising at least one of the catalyst compounds, it can be used as a catalyst for a polymerization reaction.
[102]
[Formula 3]
[103]
- [Al (R 7 ) -O] a -
[104]
[Formula 4]
[105]
A(R 7 ) 3
[106]
[Formula 5]
[107]
[LH] + [W (D) 4 ] - or [L] + [W (D) 4 ] -
[108]
In Formulas 3 to 5,
[109]
R 7 may be the same as or different from each other, and 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 an 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, a hydrocarbyl having 1 to 20 carbon atoms, an 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 acid,
[114]
W is a group 13 element,
[115]
a is an integer of 2 or more.
[116]
Examples of the compound represented by Chemical Formula 3 include alkyl aluminoxanes such as methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane, and two or more of the alkyl aluminoxanes are mixed. And modified alkylaluminoxane, specifically methylaluminoxane, and modified methylaluminoxane (MMAO).
[117]
Examples of the compound represented by Formula 4 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl 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 are included, and specifically, may be selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.
[118]
Examples of the compound represented by Formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra (o,p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenyl boron, N,N -Diethylanilinium tetraphenyl boron, N,N-diethylanilinium tetrapentafluorophenyl boron, diethyl ammonium tetrapentafluorophenyl boron, triphenylphosphonium tetraphenyl boron, trimethylphosphonium tetraphenyl boron, dimethyl Anilinium tetrakis (pentafluorophenyl) borate, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, tri Propyl ammonium tetra (p-tolyl) aluminum, triethyl ammonium tetra (o,p-dimethylphenyl) aluminum, tributyl ammonium tetra (p-trifluoromethylphenyl) aluminum, trimethyl ammonium tetra (p-trifluoromethylphenyl) aluminum , Tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatentraphenylaluminum, triphenyl Phosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropyl ammonium tetra (p-tolyl) boron, triethyl ammonium tetra (o,p-dimethylphenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) ) Boron or triphenylcarbonium tetrapentafluorophenyl boron, and the like.
[119]
The catalyst composition, as a first method, is 1) a mixture of the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 is contacted with a 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.
[120]
In addition, the catalyst composition may be prepared by contacting the compound represented by Formula 3 with the first mixture of the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 as a second method. .
[121]
In the case of the first method of 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/compound represented by Formula 3 or Formula 4 exceeds 1/2, the amount of the alkylating agent is very small There is a problem that the alkylation of is not completely proceeded, and if the molar ratio is less than 1/5,000, the alkylation of the metal compound occurs, but the alkylated metal compound due to a side reaction between the remaining excess alkylating agent and the activator, which is a compound of Formula 5 There is a problem that the activation of is not fully achieved. 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, and specifically 1/10 to 1 day It may be, and more specifically, it may be 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 to the compound represented by Formula 5 exceeds 1, the amount of the activator is relatively small, so that the metal compound is not activated. Incomplete activation of the resulting catalyst composition may decrease, and if the molar ratio is less than 1/25, activation of the metal compound is completely achieved.
[122]
In the case of the second method of 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 that the activation of the metal compound may not be completed, and thus the activity of the resulting catalyst composition may decrease. Is completely achieved, but the unit cost of the catalyst composition may not be economical or the purity of the resulting polymer may be degraded with an excess amount of activator remaining.
[123]
When preparing the catalyst composition, a hydrocarbon solvent such as pentane, hexane, or heptane, 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 form supported on a carrier.
[125]
The carrier may be used without particular limitation as long as it is used as a carrier in a metallocene catalyst. Specifically, the carrier may be silica, silica-alumina or silica-magnesia, and any one or a mixture of two or more of them may be used.
[126]
Among these, when the carrier is silica, since the functional groups of the silica carrier and the metallocene compound of Formula 1 chemically form bonds, 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 entangled during the production process of the olefin-based polymer. In addition, the olefin-based polymer produced in the presence of a 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 including 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 performed by a conventional process applied to polymerization of the olefin 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 carried out 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 may be mentioned, but not limited thereto.
[131]
The polymerization of the olefin-based polymer may be performed by reacting at a temperature of about 25 to about 500° C. and a pressure of about 1 to about 100 kgf/cm 2 .
[132]
Specifically, the polymerization of the polyolefin may be performed 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
[133]
[134]
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, wires, toys, textiles, medical, etc. It is useful for molding or injection molding, and can be particularly useful for automobiles that require excellent impact strength.
[135]
In addition, the olefin-based polymer of the present invention can be usefully used in the production of a molded article.
[136]
The molded article may be specifically a blow molded article, an inflation molded article, a cast molded article, an extrusion laminate molded article, an extrusion molded article, a foam molded article, an injection molded article, a sheet, a film, a fiber, a monofilament, or a nonwoven fabric.
Mode for carrying out the invention
[137]
Example
[138]
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art may easily implement the present invention. However, the present invention may be implemented in various different forms, and is not limited to the embodiments described herein.
[139]
[140]
Preparation Example 1: Preparation of transition metal compound 1
[141]
(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)
[142]

[143]
(i) Preparation of lithium carbamate
[144]
1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were added to a Schlenk 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 the flask was stirred for 2 hours, the temperature of the flask was raised to room temperature while removing the generated butane gas. The flask was again immersed in a -78°C low temperature bath to lower the temperature, and then CO 2 gas was added. 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 transferring the flask to a dry box, pentane was added, stirred vigorously, and filtered to obtain a white solid compound, lithium carbamate. The white solid compound is coordinated with diethyl ether. At this time, the yield is 100%.
[145]
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
[146]
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
[147]
(ii) Preparation of 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline
[148]
The lithium carbamate compound (8.47 g, 42.60 mmol) prepared in step (i) was added to a Schlenk flask. Then, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were sequentially added. After immersing the Schlenk flask in a -20°C low temperature bath made of acetone and a small amount of dry ice and stirring for 30 minutes, t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of the reaction mixture turned red. The mixture was stirred for 6 hours while maintaining -20°C. CeCl 3 · 2LiCl solution (129 mL, 0.33 M, 42.60 mmol) dissolved in tetrahydrofuran and tetramethylcyclopentinone (5.89 g, 42.60 mmol) were mixed in a syringe, and then introduced 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, followed by filtration to obtain a filtrate. After transferring the filtrate to a separatory funnel, hydrochloric acid (2 N, 80 mL) was added and shaken for 12 minutes. Then, a saturated aqueous sodium hydrogen carbonate solution (160 mL) was added to neutralize and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to remove moisture and filtered. The filtrate was taken and the solvent was removed. The obtained filtrate was purified by column chromatography using hexane and ethyl acetate (v/v, 10:1) solvent to obtain a yellow oil. The yield was 40%.
[149]
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
[150]
[151]
(2) [(1,2,3,4 -tetrahydroquinolin- 8-yl) tetramethyl cyclopentadienyl - η 5 , κ -N] titanium dimethyl ([(1,2,3,4- Tetrahydroquinolin - Preparation of 8-yl)tetramethylcyclopentadienyl-eta5,kapa-N]titanium dimethyl )
[152]

[153]
(i) [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η 5 , κ -N] Preparation of dilithium compound
[154]
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, and the temperature was lowered to -30°C, and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was slowly added while stirring. It was reacted for 6 hours while raising the temperature to room temperature. After that, it was filtered while washing several times with diethyl ether, and the solid was obtained. Vacuum was applied to remove the remaining solvent to obtain a yellow solid dilithium compound (9.83 g). The yield was 95%.
[155]
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
[156]
[157]
(ii) (1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η 5 , κ -N] Preparation of titanium dimethyl
[158]
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 MeLi (21.7 mL, 31.52 mmol, 1.4 M) was slowly added while stirring at -30°C. 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 added to 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. When vacuum was applied to remove pentane, a dark brown compound (3.70 g) was obtained. The yield was 71.3%.
[159]
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
[160]
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
[161]
[162]
Preparation Example 2: Preparation of transition metal compound 2
[163]
(1) 2- methyl- 7-(2,3,4,5- tetramethyl- 1,3 -cyclopentadienyl ) Preparation of indoline
[164]
Except for using 2-methyl indoline in place of 1,2,3,4-tetrahydroquinoline in (1) of Preparation Example 1, through the same method as in (1) of Preparation Example 1, 2 -Methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline was prepared. The yield was 19%.
[165]
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.
[166]
[167]
(2) [(2- methyl turned -7-yl) tetramethyl-cyclopentadienyl - ethanone 5, kappa -N] titanium dimethyl ([(2- Methylindolin -7- yl ) tetramethylcyclopentadienyl - eta5, kapa -N] titanium dimethyl ) production
[168]

[169]
(i) 2-methyl-7-(2,3 in place 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 in Preparation Example 1 (2) (i), except that A dilithium salt compound (compound 4 g) coordinated with 0.58 equivalent of diethyl ether was obtained (1.37 g, 50%).
[170]
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 .
[171]
[172]
(ii) A titanium compound was prepared using the dilithium salt compound (compound 4g) (1.37 g, 4.44 mmol) prepared in (i) above in the same manner as in (2)(ii) of Preparation Example 1.
[173]
1 H NMR (C 6 D 6 ): δ 7.01-6.96 (m, 2H, CH), δ 6.82 (t, J=7.4Hz, 1H, CH), δ
[174]
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.
[175]
[176]
Example 1
[177]
After filling a 1.5L continuous process reactor with hexane solvent (5 kg/h) and 1-octene (1.5 kg/h), the temperature at the top of the reactor was preheated to 140.7°C. Triisobutylaluminum compound (0.05 mmol/min), a mixture of the transition metal compound 1 obtained in Preparation Example 1 and the transition metal compound 2 obtained in Preparation Example 2 at a molar ratio of 1:3 (0.5 μmol /min), and dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (1.5 μmol/min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg/h) was added into the reactor and maintained at 140.7°C for 30 minutes or longer in a continuous process at a pressure of 89 bar to proceed with a copolymerization reaction to obtain a copolymer. After drying for 12 hours or more in a vacuum oven, the physical properties were measured.
[178]
[179]
Examples 2 to 6
[180]
In the same manner as in Example 1, the copolymerization reaction was carried out using two transition metal catalysts. The reaction proceeded to obtain a copolymer.
[181]
[182]
Comparative Example 1
[183]
SK's Solumer851L was purchased and used.
[184]
[185]
Comparative Example 2
[186]
Dow's EG8842 was purchased and used.
[187]
[188]
Comparative Example 3
[189]
A copolymer was obtained by performing a copolymerization reaction in the same manner as in Example 1, except that only the transition metal compound 1 was used as a catalyst.
[190]
[191]
Comparative Example 4
[192]
A copolymer was obtained by performing a copolymerization reaction in the same manner as in Example 1, except that only the transition metal compound 2 was used as a catalyst.
[193]
[194]
Comparative Example 5
[195]
In the same manner as in Example 1, the copolymerization reaction was carried out using two transition metal catalysts. The reaction proceeded to obtain a copolymer.
[196]
[197]
[Table 1]
Catalyst (μmol/min) Catalyst ratio (transition metal compound 1:2) Cocatalyst (μmol/min) TiBAl(mmol/min) Ethylene (kg/h) 1-octene (kg/h) Reaction temperature (℃)
Example 1 0.5 1:3 1.5 0.05 0.87 5 140.7
Example 2 0.55 1:3 1.65 0.6 0.87 5 145.2
Example 3 0.55 1:2 1.65 0.5 0.87 5 144.5
Example 4 0.5 1:3 1.5 0.04 0.87 5 140.7
Example 5 0.28 1:3 1.65 0.5 0.87 5 150.6
Example 6 0.42 1:1 1.2 0.5 0.87 3 148.1
Comparative Example 1 0.5 - 1.5 0.05 0.87 5 140.7
Comparative Example 2 0.55 - 1.65 0.6 0.87 5 145.2
Comparative Example 3 0.2 - 0.35 0.04 0.87 5 139
Comparative Example 4 0.38 - 1.14 0.05 0.87 5 135.7
Comparative Example 5 0.27 1:8 0.81 0.04 0.87 1.3 141.5
[198]
Experimental Example 1
[199]
The physical properties of the copolymers of Examples 1 to 6 and Comparative Examples 1 to 5 were evaluated according to the following method, and are shown in Table 2 below.
[200]
[201]
1) Density of polymer
[202]
Measured by ASTM D-792.
[203]
2) Melt Index (MI) of polymer
[204]
It was measured according to ASTM D-1238 [Condition E, MI 10 (190°C, 10kg load), MI 2.16 (190°C, 2.16kg load)].
[205]
3) Weight average molecular weight (Mw, g/mol) and molecular weight distribution (MWD)
[206]
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.
[207]
-Column: PL Olexis
[208]
-Solvent: Trichlorobenzene (TCB)
[209]
-Flow rate: 1.0 ml/min
[210]
-Sample concentration: 1.0 mg/ml
[211]
-Injection volume: 200 µl
[212]
-Column temperature: 160℃
[213]
-Detector: Agilent High Temperature RI detector
[214]
-Standard: Polystyrene (corrected by 3rd order function)
[215]
4) Melting point of polymer (Tm)
[216]
It was obtained using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 6000) manufactured by PerKinElmer. That is, after the temperature was increased to 200°C, the temperature was maintained at that temperature for 1 minute, then decreased to -100°C, and the temperature was increased again to set the top of the DSC curve 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.
[217]
5) Soluble Fraction, the weight average molecular weight (Mw) of the soluble fraction, and the elution end temperature
[218]
CFC of PolymerChar was used as the measuring equipment. First, the 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. Then, the temperature of the TREF column was lowered to -20°C at a rate of 0.5°C/min, and then maintained at -20°C for 10 minutes. Then, the elution amount (mass %) was measured using an infrared spectrophotometer. Then, raising the temperature of the TREF column to a preset temperature at a rate of 20°C/mi, and maintaining the temperature at the temperature reached for a preset time (ie, about 27 minutes), the TREF temperature is 130°C. It was repeated until this time, and the amount (mass %) of the eluted fraction was determined during each temperature range. In addition, the molecular weight Mw was measured in the same manner as the GPC measurement principle, except that the fraction eluted at each temperature was sent to a GPC column and o-dichlorobenzene was used as a solvent.
[219]
The content of the ultra-low crystalline region refers to the content of the fraction eluted below -20°C, and the molecular weight Mw was measured using a CFC GPC column. The elution end temperature was defined as the final temperature at which no more fractions were eluted in the detector.
[220]
[221]
[Table 2]
Density (g/mL) MI 2.16 (g/10min) Tm(℃) Mw MWD SF (CFC) (% by weight) Elution end temperature (℃) Mw of SF
Example 1 0.856 1.07 32.5 131K 2.29 27.5 31 104827
Example 2 0.859 0.97 (MI 10 7.86) 38.7 128K 2.08 16.8 34 82474
Example 3 0.857 1.10 35.2 122K 2.08 25.3 31 60064
Example 4 0.855 1.74 28.9 112K 2.15 40.7 28 161537
Example 5 0.861 1.02 (MI 10 10.4) 42.2 126K 2.16 10.7 40 102736
Example 6 0.860 1.20 41.8 119K 2.22 12.6 38 75326
Comparative Example 1 0.859 1.06 44.4 130K 2.36 14.6 34 40675
Comparative Example 2 0.859 0.95 43.1 132K 2.02 5.3 52 135552
Comparative Example 3 0.858 1.44 36.3 120K 2.01 5.8 37 191817
Comparative Example 4 0.861 1.19 38.8 124K 2.03 1.4 40 50581
Comparative Example 5 0.861 0.59 44.5 154K 2.32 5.5 76.0 43971
[222]
In Table 2, the elution end temperature is defined as the final temperature at which the fraction is no longer eluted by the detector, and the low elution end temperature is a low-density olefin that is distinguished from polymers with high density or high crystallinity such as LDPE, HDPE, LLDPF, etc. It is a general characteristic of the polymer.
[223]
In Table 2, the greater the amount of SF (>8%), the better the impact strength during compounding, but it is a very difficult technique to increase the SF content by more than a certain amount at the same density. This adversely affects the anti-blocking properties. The copolymer of the example has excellent impact strength and anti-blocking properties by maintaining a high SF content while maintaining a high molecular weight of the fraction.
[224]
[225]
Experimental Example 2
[226]
50 g of the pellets of the copolymers prepared in Example 2 and Comparative Examples 1 and 2, respectively, were taken and placed in an 8 cm × 10 cm zipper bag, and a hole was punched out with a needle to bleed air and then compressed. A zipper bag was placed in the central part away from the bottom of the chamber, and a load was applied with 2 kg weight x 2 pieces on top. The chamber temperature program was operated and left at 35°C for 7 hours, -5°C for 5 hours, and 0°C for 5 hours, and 0°C was maintained. After that, the degree of blocking was checked.
[227]
In addition, PDMS (polydimethylsiloxane, XIAMETER® MEM-0039 Emulsion, Dow-Corning / PDMS 35wt%), a commonly used surface treatment agent by taking 50 g of the pellets of the copolymers each prepared in Example 2 and Comparative Example 1 And Ca-st (calcium stearate, SC-130, Songwon Industries) were prescribed 700 ppm and 450 ppm, respectively, placed in an 8 cm × 10 cm zipper bag, and punched through a hole with a needle to bleed air and compressed.
[228]
A zipper bag was placed in the central part away from the bottom of the chamber, and a load was applied with 2 kg weight x 2 pieces on top. The chamber temperature program was operated and left at 35°C for 7 hours, -5°C for 5 hours, and 0°C for 5 hours, and 0°C was maintained. After that, the degree of blocking was checked.
[229]
In addition, 50 g of the pellets of the copolymers each prepared in Example 2 and Comparative Example 2 were taken and 4,000 ppm of talc (Talc, KCM6300), which is a commonly used surface treatment agent, was prescribed, and put in an 8 cm × 10 cm zipper bag with a needle. A hole was drilled to bleed air and compressed.
[230]
A zipper bag was placed in the central part away from the bottom of the chamber, and a load was applied with 2 kg weight x 2 pieces on top. The chamber temperature program was operated and left at 35°C for 7 hours, -5°C for 5 hours, and 0°C for 5 hours, and 0°C was maintained. After that, the degree of blocking was checked.
[231]
The evaluation criteria are shown in Table 3 below, and the experimental results are shown in Table 4 below.
[232]
[Table 3]
Rating state
0 Spills when the zipper bag is opened and turned over
One Loosening in the process of removing zipper
2 The lump from the zipper bag disintegrates within 20 seconds
3 Disintegrates when pressed by hand
4 Disintegrates when pressed with strong force
5 Does not disintegrate when pressed by hand
[233]
[Table 4]
Type of copolymer Type of surface treatment agent (use, ppm) Blocking evaluation
PDMS Ca-St Talc
Example 2 - - - 4
700 450 One
4,000 One
Comparative Example 1 - - - 5
700 450 - 3
Comparative Example 2 - 4000 5
[234]
Referring to Table 4, when the copolymers of Example 2 and Comparative Example 1 were not treated with a separate surface treatment agent, it was confirmed that the copolymer of Example 2 had more excellent anti-blocking properties. In addition, when PDMS and Ca-st, which are surface treatment agents commonly used as anti-blocking agents, were prescribed for the copolymers of Example 2 and Comparative Example 1, the copolymer of Example 2 also had better anti-blocking properties. This was also the case when talc was treated with a surface treatment agent.
[235]
Accordingly, it was confirmed that the copolymer of Example 2 exhibited superior anti-blocking performance compared to the copolymer of Comparative Example 1 under both the condition that the surface treatment agent was not used and the same surface treatment agent was prescribed.
Claims
[Claim 1]
(1) the density (d) is 0.850 to 0.865 g/cc, (2) the melt index (Melt Index, MI, 190° C., 2.16 kg load condition) is 0.1 g/10 min to 3.0 g/10 min, ( 3) On cross-fraction chromatography (CFC, Cross-fractionation Chromatography), the soluble fraction (SF, Soluble Fraction) at -20°C is 8% by weight or more, and the weight average molecular weight (Mw) of the fraction is from 50,000 g/mol to 500,000 g/mol, an olefin-based polymer.
[Claim 2]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer has a weight average molecular weight (Mw) of 50,000 g/mol to 300,000 g/mol of a soluble fraction at -20°C on the cross-fraction chromatography.
[Claim 3]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer has a weight average molecular weight (Mw) of 60,000 g/mol to 200,000 g/mol of the soluble fraction at -20°C on the cross-fraction chromatography.
[Claim 4]
The olefin-based polymer of claim 1, wherein the olefin-based polymer (4) has a molecular weight density (MWD) of 1.0 to 3.0.
[Claim 5]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer (5) has a weight average molecular weight (Mw) of 10,000 to 500,000.
[Claim 6]
The olefin-based polymer according to claim 1, wherein the (2) melt index (MI) is 0.2 g/10 min to 2 g/10 min.
[Claim 7]
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 8]
The method of claim 7, wherein the alpha-olefin comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undee Sen, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-itocene, norbornene, novonadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4 -Olefins 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 9]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer is a copolymer of ethylene and 1-octene.
[Claim 10]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer has an elution end temperature of 60°C or less.
[Claim 11]
The olefin-based polymer according to claim 1, wherein the soluble fraction (SF, Soluble Fraction) at -20°C on cross-fractionation chromatography (CFC) is 10% or more.
[Claim 12]
The olefin-based polymer of claim 1, wherein the olefin-based polymer has (4) a molecular weight density (MWD) of 1.0 to 3.0, and (6) MI 10 /MI 2.16 >7.91 (MI 2.16 ) -0.188 . .
[Claim 13]
The method of claim 1, wherein the olefin-based polymer is in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of Formula 1 and a transition metal compound of Formula 2 in an equivalent ratio of 1:1 to 1:5. An olefin-based polymer obtained by a method comprising the step of polymerizing a monomer: [Formula 1] In Formula 1, R 1 is 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 , and the two R 1s are alkyl having 1 to 20 carbon atoms or 6 to carbon atoms May be linked to each other by an alkylidine radical containing 20 aryl radicals to form a ring; R 2 are the same as or different from each other, and each independently hydrogen; halogen; Alkyl of 1 to 20 carbon atoms; Aryl; Alkoxy; Aryloxy; An amido radical, and two or more of R 2 may be linked 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 of 1 to 20 carbon atoms; Or a nitrogen-containing aliphatic or aromatic ring substituted or unsubstituted with an aryl radical, and when the number of substituents is 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 of 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; [Chemical 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, and 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. There is; R 5 are the same as or different from each other, and each independently hydrogen; halogen; Alkyl of 1 to 20 carbon atoms; Aryl; Alkoxy; Aryloxy; Is an amido radical, wherein R Two or more of 2 may be connected 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 of 1 to 20 carbon atoms; Or a nitrogen-containing aliphatic or aromatic ring substituted or unsubstituted with an aryl radical, and when the number of the substituents is plural, two or more substituents among the substituents may be linked 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 of 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 14]
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 in the presence of the catalyst composition for olefin polymerization.