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. 10-2019-0121152 dated September 30, 2019, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
[Technical field]
[4]
The present invention relates to an olefin-based polymer, and more particularly, to a low-density olefin-based polymer having 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 the disadvantage of very low polymerization activity. For this reason, although a method of protecting a polar group with a protecting group has been implemented, when 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. there is.
[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 (3).
[16]
(1) Melt Index (MI, 190°C, 2.16 kg load condition) is 0.1 g/10 min to 10.0 g/10 min, (2) Density (d) is 0.860 g/cc to 0.880 g/cc, (3) T(90)-T(50)≤50, T(95)-T(90)≥10, when measuring differential scanning calorimetry (SSA);
[17]
where T(50), T(90) and T(95) are respectively 50%, 90%, and 95% melting when the temperature-heat capacity curve is fractionated from the differential scanning calorimetry precision measurement (SSA) measurement result, respectively. is the temperature
Effects of the Invention
[18]
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
[19]
1 is a graph showing the results of measuring the melting temperature of the polymer of Example 1 using a differential scanning calorimeter (DSC).
[20]
2 is a graph showing the results of measuring the melting temperature of the polymer of Comparative Example 1 using a differential scanning calorimeter (DSC).
[21]
3 is a graph showing the results of measurement of the polymer of Example 1 by differential scanning calorimetry (SSA).
[22]
4 is a graph showing the results of measurement of the polymer of Comparative Example 1 by differential scanning calorimetry precision measurement (SSA).
[23]
FIG. 5 is a graph showing T(50), T(90), and T(95) for the polymer of Example 1 after fractionation of results measured by differential scanning calorimetry (SSA).
[24]
6 is a graph showing T(50), T(90), and T(95) of the polymer of Comparative Example 1 after fractionation of results measured by differential scanning calorimetry (SSA).
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 (3).
[30]
(1) Melt Index (MI, 190°C, 2.16 kg load condition) is 0.1 g/10 min to 10.0 g/10 min, (2) Density (d) is 0.860 g/cc to 0.880 g/cc, (3) T(90)-T(50)≤50 and T(95)-T(90)≥10 in differential scanning calorimetry precision measurement (SSA).
[31]
where T(50), T(90) and T(95) are respectively 50%, 90%, and 95% melting when the temperature-heat capacity curve is fractionated from the differential scanning calorimetry precision measurement (SSA) measurement result, respectively. is the temperature
[32]
The olefin-based polymer according to the present invention has an ultra-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). When it has, it exhibits higher tensile strength and tear strength. 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 0.860 g / cc to 0.880 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 0.850 g/cc to 0.890 g/cc, specifically 0.850 g/cc to 0.880 g/cc, and more specifically 0.860 g/cc to 0.875 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 T(90)-T(50)≤50, T(95)-T(90)≥10, and specifically 20≤T(90) when measured by differential scanning calorimetry (SSA). )-T(50)≤45, and may be 10≤T(95)-T(90)≤30, more specifically 30≤T(90)-T(50)≤40, and 10≤T(95) )-T(90)≤20.
[38]
The T(50), T(90) and T(95) are respectively 50%, 90%, and 95% melted when the temperature-heat capacity curve is fractionated from the differential scanning calorimetry precision measurement (SSA) measurement result, respectively. is the temperature
[39]
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).
[40]
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).
[41]
In addition, the olefin-based polymer according to an example of the present invention may further satisfy the requirement of (4) 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).
[42]
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) (5) 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.
[43]
[44]
In addition, the olefin-based polymer according to an example of the present invention may additionally satisfy the requirement of (6) a melting point (Tm) of 20°C to 70°C when measured by differential scanning calorimetry (DSC), and the melting point (Tm) is specifically 25 It may be ℃ to 60 ℃, more specifically 25 ℃ to 50 ℃ may be.
[45]
[46]
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.
[47]
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, 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.
[48]
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.
[49]
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 weight %, and more specifically, it may be 20 weight % to 50 weight %. When the alpha-olefin is included in the above range, it is easy to implement the above-described physical properties.
[50]
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.
[51]
In an example of the present invention, the amount of hydrogen gas added may be 0.35 to 3 parts by weight, specifically 0.4 to 2 parts by weight, and more specifically 0.45 to 1.5 parts by weight, based on 1 part by weight of the olefinic monomer added to the reaction system. can be negative In addition, in an example of the present invention, when the olefin-based polymer is polymerized by continuous solution polymerization, the hydrogen gas is 0.35 to 3 kg/h, specifically 0.4, based on 1 kg/h of the olefinic monomer introduced into the reaction system. to 2 kg/h, more specifically 0.45 to 1.5 kg/h.
[52]
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 0.8 to 3 parts by weight, specifically 0.9 to 2.8 parts by weight, based on 1 part by weight of ethylene, More specifically, it may be added in an amount of 1 to 2.7 parts by weight. In addition, in an example of the present invention, when the olefin-based polymer is a copolymer of ethylene and alpha-olefin, and polymerized by continuous solution polymerization, the hydrogen gas is 0.8 to 1 kg/h of ethylene introduced into the reaction system. 3 kg/h, specifically 0.9 to 2.8 kg/h, more specifically 1 to 2.7 kg/h.
[53]
When the polymerization is performed under the conditions in which the hydrogen gas is introduced in an amount within the above range, the olefin-based polymer of the present invention may satisfy the above-described physical properties.
[54]
Specifically, the olefin-based copolymer of the present invention is obtained by a manufacturing method comprising the step of polymerizing an olefinic monomer by introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of Formula 1 below can get
[55]
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 should be understood to include equivalents and substitutes.
[56]
[Formula 1]
[57]

[58]
In Formula 1,
[59]
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;
[60]
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;
[61]
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;
[62]
M is a Group 4 transition metal;
[63]
Q 1 and Q 2 are each independently halogen; alkyl having 1 to 20 carbon atoms; alkenyl; aryl; alkylaryl; arylalkyl; alkyl amido having 1 to 20 carbon atoms; aryl amido; or an alkylidene radical having 1 to 20 carbon atoms.
[64]
[65]
In addition, in another example of the present invention, in Formula 2, 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,
[66]
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;
[67]
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,
[68]
M may be a Group 4 transition metal.
[69]
[70]
The transition metal compound represented by Formula 2 has a metal site connected by a cyclopentadienyl ligand into which tetrahydroquinoline is introduced, and thus the Cp-MN angle is structurally narrow, 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
[71]
[72]
Each of the substituents defined in the present specification will be described in detail as follows.
[73]
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.
[74]
As used herein, the term 'halogen' means fluorine, chlorine, bromine or iodine, unless otherwise specified.
[75]
The term 'alkyl' as used herein, unless otherwise specified, refers to a straight-chain or branched hydrocarbon residue.
[76]
As used herein, the term 'cycloalkyl' refers to cyclic alkyl including cyclopropyl and the like, unless otherwise specified.
[77]
As used herein, the term 'alkenyl' refers to a straight-chain or branched alkenyl group, unless otherwise noted.
[78]
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.
[79]
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.
[80]
The alkylaryl group means an aryl group substituted by the alkyl group.
[81]
The arylalkyl group means an alkyl group substituted by the aryl group.
[82]
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.
[83]
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.
[84]
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.
[85]
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.
[86]
[87]
The compound of Formula 1 may be of Formula 1-1, but is not limited thereto.
[88]
[Formula 1-1]
[89]

[90]
In addition, it may be a compound having various structures within the range defined in Formula 1 above.
[91]
[92]
Since the transition metal compound of Formula 2 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. .
[93]
The transition metal compound of Formula 1 may be prepared by the following method as an example.
[94]
[Scheme 1]
[95]

[96]
In Scheme 1, R 1 to R 3 , M, Q 1 and Q 2 are as defined in Formula 1 above.
[97]
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.
[98]
[99]
The transition metal compound of Formula 1 may be used as a catalyst for a polymerization reaction 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.
[100]
[Formula 2]
[101]
-[Al(R 4 )-O] a -
[102]
[Formula 3]
[103]
A(R 4 ) 3
[104]
[Formula 4]
[105]
[LH] + [W(D) 4 ] - or [L] + [W(D) 4 ] -
[106]
In Formulas 2 to 3,
[107]
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,
[108]
A is aluminum or boron,
[109]
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,
[110]
H is a hydrogen atom,
[111]
L is a neutral or cationic Lewis base,
[112]
W is a group 13 element,
[113]
a is an integer greater than or equal to 2;
[114]
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).
[115]
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.
[116]
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, diethylammoniumtetrapentafluorophenylaluminum, triphenyl Phosphonium tetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, triphenylcarboniumtetra(p-trifluoromethylphenyl) ) boron or triphenylcarboniumtetrapentafluorophenylboron.
[117]
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.
[118]
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.
[119]
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.
[120]
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 from 1/100 to 1/100, and more specifically, from 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.
[121]
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.
[122]
In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a supported form on a carrier.
[123]
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.
[124]
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.
[125]
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.
[126]
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 .
[127]
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.
[128]
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.
[129]
The 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
[130]
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.
[131]
In addition, the olefin-based polymer of the present invention may be usefully used in the manufacture of a molded article.
[132]
Specifically, the molded article may be a blow molding molded article, an inflation molded article, a cast molded article, an extrusion laminate molded article, an extrusion molded article, an expanded molded article, an injection molded article, a sheet, a film, a fiber, a monofilament, or a nonwoven fabric.
Modes for carrying out the invention
[133]
Example
[134]
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.
[135]
[136]
Preparation Example 1: Preparation of transition metal compound A
[137]

[138]
(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)
[139]
(i) Preparation of lithium carbamate
[140]
1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were placed in a shlenk flask. The Schlenk flask was immersed in a -78°C low temperature bath made of dry ice and acetone and stirred for 30 minutes. Then, n-BuLi (39.3 mL, 2.5 M, 98.24 mmol) was injected into a syringe under a nitrogen atmosphere, and a pale yellow slurry was formed. Then, after stirring the flask for 2 hours, the temperature of the flask was raised to room temperature while removing the butane gas produced. The flask was again immersed in a low temperature bath at -78° C. to lower the temperature, and then CO 2 gas was introduced. As the carbon dioxide gas was added, the slurry disappeared and became a transparent solution. The flask was connected to a bubbler and the temperature was raised to room temperature while removing carbon dioxide gas. After that, excess CO 2 gas and solvent were removed under vacuum. After moving the flask to a dry box, pentane was added, stirred vigorously, and filtered to obtain lithium carbamate, a white solid compound. The white solid compound is coordinated with diethyl ether. In this case, the yield is 100%.
[141]
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
[142]
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
[143]
(ii) Preparation of 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline
[144]

[145]
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 a yellow oil. The yield was 40%.
[146]
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
[147]
[148]
(2) [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η 5 , κ -N] titanium dimethyl ([(1,2,3,4-Tetrahydroquinolin- Preparation of 8-yl)tetramethylcyclopentadienyl-eta5,kapa-N]titanium dimethyl)
[149]

[150]
(i) Preparation of [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η 5 , κ -N]dilithium compound
[151]
8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (8.07 g) prepared through step (1) in a dry box , 32.0 mmol) and 140 mL of diethyl ether were placed in a round flask, the temperature was lowered to -30°C, and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was slowly added with stirring. The reaction was carried out for 6 hours while raising the temperature to room temperature. After that, it was filtered while washing with diethyl ether several times to obtain a solid. A vacuum was applied to remove the remaining solvent to obtain a dilithium compound (9.83 g) as a yellow solid. The yield was 95%.
[152]
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
[153]
[154]
(ii) (1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl- η 5 , κ -N] Preparation of titanium dimethyl
[155]
In a dry box, TiCl 4 ·DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL) were placed in a round flask, and while stirring at -30°C, MeLi (21.7 mL, 31.52 mmol, 1.4 M) was slowly added thereto. After stirring for 15 minutes, [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- ηη 5 , κ -N]dilithium compound prepared in step (i) ( 5.30 g, 15.76 mmol) was placed in a 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 the pentane was removed by vacuum, a dark brown compound (3.70 g) was obtained. The yield was 71.3%.
[156]
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
[157]
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
[158]
[159]
Preparation Example 2: Preparation of transition metal compound B
[160]

[161]
(1) Preparation of 2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline
[162]
Through the same method as (1) of Preparation Example 1, except that 2-methyl indoline was used instead of 1,2,3,4-tetrahydroquinoline in (1) of Preparation Example 1, 2 -Methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline was prepared. The yield was 19%.
[163]
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.
[164]
[165]
(2) [(2-Methylindolin-7-yl)tetramethylcyclopentadienyl-eta5,kappa-N]titanium dimethyl ([(2-Methylindolin-7-yl)tetramethylcyclopentadienyl-eta5,kapa-N] production of titanium dimethyl)
[166]
(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 (2) (i) of Preparation Example 1, except that A dilithium salt compound (compound 4 g) coordinated with 0.58 equivalents of diethyl ether was obtained (1.37 g, 50 %).
[167]
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 .
[168]
[169]
(ii) A titanium compound was prepared in the same manner as in (2)(ii) of Preparation Example 1 with the dilithium salt compound (compound 4g) (1.37 g, 4.44 mmol) prepared in (i) above.
[170]
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
[171]
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.
[172]
[173]
Example 1
[174]
After charging a 1.5 L continuous process reactor with hexane solvent (5 kg/h) and 1-butene (0.95 kg/h), the temperature at the top of the reactor was preheated to 140.7°C. Triisobutylaluminum compound (0.06 mmol/min), transition metal compound B obtained in Preparation Example 2 (0.40 μmol/min), and dimethylanilinium tetrakis (pentafluorophenyl) borate promoter (1.20 μmol/min) were simultaneously introduced into the reactor. Then, hydrogen gas (15 cc/min) and ethylene (0.87 kg/h) were introduced into the reactor and maintained at 141° 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.
[175]
[176]
Examples 2 to 5
[177]
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.
[178]
[179]
Comparative Example 1
[180]
DF610 from Mitsui Chemicals was purchased and used.
[181]
[182]
Comparative Examples 2 to 4
[183]
The copolymerization reaction was carried out in the same manner as in Example 1, and the type of transition metal compound, the amount of the transition metal compound, the amount of catalyst and co-catalyst, and the reaction temperature, the amount of hydrogen input, and the amount of comonomer were changed as shown in Table 1 below. to proceed with the copolymerization reaction to obtain a copolymer.
[184]
[185]
Comparative Example 5
[186]
DF710 from Mitsui Chemicals was purchased and used.
[187]
[188]
Comparative Example 6
[189]
DF640 from Mitsui Chemicals was purchased and used.
[190]
[191]
Comparative Example 7
[192]
Dow's EG7447 was purchased and used.
[193]
[194]
[Table 1]
Catalyst type 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 transition metal compound B 0.40 1.20 0.06 0.87 5 0.95 15 141
Example 2 transition metal compound B 0.60 1.80 0.05 0.87 7 0.93 32 145
Example 3 transition metal compound B 0.45 1.35 0.04 0.87 7 0.75 15 145
Example 4 transition metal compound B 0.74 2.22 0.05 0.87 7 0.93 25 150
Example 5 transition metal compound B 0.55 1.65 0.04 0.87 7 0.84 38 148
Comparative Example 2 transition metal compound B 0.78 2.34 0.06 0.87 5 1.15 - 161
Comparative Example 3 transition metal compound A 0.32 0.96 0.05 0.87 5 0.62 - 145
Comparative Example 4 transition metal compound B 0.50 1.50 0.06 0.87 5 1.15 10 161
[195]
Experimental Example 1
[196]
The copolymers of Examples 1 to 5 and Comparative Examples 1 to 4 were evaluated for physical properties according to the following method, and are shown in Tables 2 and 3 below.
[197]
1) Density of polymer
[198]
Measured by ASTM D-792.
[199]
2) Polymer Melt Index (MI)
[200]
It was measured by ASTM D-1238 (Condition E, 190°C, 2.16 kg load).
[201]
3) Weight average molecular weight (Mw, g/mol) and molecular weight distribution (MWD)
[202]
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.
[203]
- Column: PL Olexis
[204]
- Solvent: TCB (Trichlorobenzene)
[205]
- Flow rate: 1.0 ml/min
[206]
- Sample concentration: 1.0 mg/ml
[207]
- Injection volume: 200 μl
[208]
- Column temperature: 160℃
[209]
- Detector: Agilent High Temperature RI detector
[210]
- Standard: Polystyrene (corrected by cubic function)
[211]
4) Melting point of polymer (Tm)
[212]
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, the top of the DSC curve was used as the melting point. At this time, the rate of temperature rise and fall is 10° C./min, and the melting point is obtained while the second temperature rises.
[213]
The DSC graph of the polymer of Example 1 is shown in FIG. 1, and the DSC graph of the polymer of Comparative Example 1 is shown in FIG. 2, respectively.
[214]
5) High-temperature melting peaks of polymers and T(95), T(90), T(50)
[215]
The differential scanning calorimeter (DSC: Differential Scanning Calorimeter 250) manufactured by TA Instruments was obtained by SSA (Successive self-nucleation/annealing) measurement method.
[216]
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.
[217]
In the last cycle, the heat capacity was specified while increasing the temperature to 150°C.
[218]
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 is melted is defined as T(50), the temperature at which 90% is melted is defined as T(90), and the temperature at which 95% is melted is defined as T(95).
[219]
The SSA graph of the polymer of Example 1 is shown in FIG. 3, and the SSA graph of the polymer of Comparative Example 1 is shown in FIG. 4, respectively.
[220]
Fig. 5 shows a graph obtained by fractionating the SSA result of the polymer of Example 1, and Fig. 4 is a graph obtained by segmenting the SSA result of the polymer of Comparative Example 1, respectively.
[221]
[222]
6) Hardness (shore A)
[223]
Hardness was measured according to ASTM D2240 standard using TECLOCK's GC610 STAND for Durometer and Mitutoyo's Shore Durometer Type A.
[224]
[225]
7) Polymer tensile strength and tear strength
[226]
The olefinic copolymers of Example 1 and Comparative Examples 1 to 3 were each extruded to prepare pellets, and then tensile strength and tear strength at breakage were measured according to ASTM D638 (50 mm/min).
[227]
[Table 2]
Density
(g/mL) MI
(g/
10min) Mw
(g/mol) MWD DSC SSA
Tm
(℃) T(50) T(90) T(95) T(90)-T(50) T(95)-T(90)
Example 1 0.862 1.20 106,000 2.01 32.1 16.0 51.1 67.6 35.1 16.5
Example 2 0.866 4.39 69,070 2.07 33.0 19.8 57.4 83.8 37.6 26.4
Example 3 0.872 1.22 99,068 2.05 45.9 31.1 61.9 73.0 30.8 11.1
Example 4 0.866 3.30 70,000 2.11 37.8 22.9 54.6 64.9 31.7 10.3
Example 5 0.865 5.10 75,388 2.09 37.2 23.1 54.1 65.3 31.0 11.2
Comparative Example 1 0.861 1.32 105,000 1.98 39.7 20.1 48.4 54.6 28.3 6.2
Comparative Example 2 0.861 1.12 102,000 2.11 28.6 14.7 46.0 54.9 31.3 8.9
Comparative Example 3 0.862 1.20 91,419 2.18 28.5 15.7 46.6 55.3 30.9 8.7
Comparative Example 4 0.862 1.23 100,423 2.185 29.9 15.0 47.8 54.2 32.8 6.4
Comparative Example 5 0.869 1.20 92,000 2.04 49.3 32.3 57.1 64.4 24.8 7.3
Comparative Example 6 0.865 3.40 71,000 2.04 43.8 21.5 54.2 57.8 32.7 3.6
Comparative Example 7 0.868 5.10 76,735 2.14 44.2 23.2 54.6 61.9 31.4 7.3
[228]
[Table 3]
Density
(g/mL) MI
(g/10min) DSC SSA tensile strength tear strength Hardness
(Shore A)
Tm
(℃) T(90)
-T(50) T(95)
-T(90)
Example 1 0.862 1.20 32.1 35.1 16.5 2.2 29.5 55.0
Comparative Example 1 0.861 1.32 39.7 28.3 6.2 2.1 25.6 56.7
Comparative Example 2 0.861 1.12 28.6 31.3 8.9 1.6 22.4 52.9
Comparative Example 3 0.862 1.20 28.5 30.9 8.7 1.3 16.7 51.6
[229]
When comparing Example 1 and Comparative Example 1 having the same level of density and MI, FIGS. 1 and 2 measured by DSC show a similar trend and show a similar graph form, so no significant difference was confirmed, but measured by SSA 3 and 4, it can be seen that there is a large difference in the high temperature region of 75° C. or higher. Specifically, Example 1 shows a peak at 75° C. or higher, whereas Comparative Example does not. Comparative Example 2 and Comparative Example 3 had a peak in the corresponding region, but the size was smaller than that of the Example. In Examples 1 to 5, T(90)-T(50)≤50 due to the difference in melting in this high-temperature region. It can be seen that T(95)-T(90)≥10 may be satisfied, and T(95)-T(90) has a wider value than 7 in Comparative Example 1.
[230]
Through Table 3, the mechanical strength of Example 1 and Comparative Examples 1, 2, and 3 having an equivalent level of density and MI can be compared. It can be seen that in Example 1, a polymer melted at a high temperature was introduced to increase mechanical rigidity, and thus tensile strength and tear strength were increased compared to Comparative Examples 1 to 3.
[231]
[232]
Examples 1 to 5 are polymers obtained by polymerizing an olefinic monomer by introducing hydrogen gas, and a high crystallinity region is introduced to satisfy T(90)-T(50)≤50, and also T(95)-T( 90) ≥ 10, indicating high mechanical rigidity. Through comparison with Comparative Examples 2 and 4, whether T(90)-T(50)≤50 and T(95)-T(90)≥10 are satisfied depending on whether hydrogen gas is input during polymerization and the amount of the input And it was confirmed that the mechanical stiffness is different.
[233]
[234]
In addition, when the olefin-based polymer of the present invention is included in the polypropylene-based composite, it is possible to provide a polypropylene-based composite capable of exhibiting significantly improved impact strength along with excellent mechanical strength. Experimental examples in which the olefin-based polymer of the present invention is applied to a polypropylene-based composite are shown below.
[235]
[236]
Composite Material Preparation Example 1: Preparation of polypropylene-based composite material
[237]
To 20 parts by weight of the olefin copolymer prepared in Example 1, 60 parts by weight of a high crystalline impact copolymer polypropylene (CB5230, manufactured by Daehan Chemical Co., Ltd.) having a melt index (230° C., 2.16 kg) of 30 g/10 min and talc (KCNAP-400™, Kotsu Corporation) (average particle diameter (D 50 ) = 11.0 μm) 20 parts by weight were added, and 0.1 parts by weight of AO1010 (Irganox 1010, Ciba Specialty Chemicals) as an antioxidant, tris(2,4-di-) After adding 0.1 parts by weight of tert-butylphenyl) phosphite (A0168) and 0.3 parts by weight of calcium stearate (Ca-st), melt kneading using a twin-screw extruder to prepare a polypropylene-based composite compound in the form of pellets did At this time, the twin screw extruder had a diameter of 25Φ, a ratio of diameter to length of 40, a barrel temperature of 200° C. to 230° C., a screw rotation speed of 250 rpm, and an extrusion amount of 25 kr/hr.
[238]
[239]
Composite Material Preparation Examples 2 to 5: Preparation of polypropylene-based composite material
[240]
A polypropylene-based composite was prepared in the same manner as in Example 1, except that the olefin copolymer as shown in Table 4 was used instead of the olefin copolymer prepared in Example 1. In this case, in Example 5, the type of polypropylene and the ratio of the olefin copolymer to the polypropylene were different. The polypropylene represented by CB5290 in Table 4 below is a high crystalline impact copolymer polypropylene (CB5290, manufactured by Daehan Petrochemical) having a melt index (230° C., 2.16 kg) of 90 g/10 min.
[241]
[242]
Comparative Preparation of Composites Examples 1 to 7: Preparation of polypropylene-based composites
[243]
A polypropylene-based composite was prepared in the same manner as in Example 1, except that the olefin copolymer as shown in Table 4 was used instead of the olefin copolymer prepared in Preparation Example 1. In this case, in Comparative Example 7, the type of polypropylene and the ratio of the olefin copolymer to the polypropylene were different.
[244]
The polypropylene represented by CB5290 in Table 4 below is a high crystalline impact copolymer polypropylene (CB5290, manufactured by Daehan Petrochemical) having a melt index (230° C., 2.16 kg) of 90 g/10 min.
[245]
[246]
[Table 4]
Olefin
polymer polypropylene mixing ratio
Olefin-based
polymer
(wt%) PP
(wt%) Talc
(wt%)
Composite Preparation Example 1 Example 1 CB5230 20 60 20
Composite Preparation Example 2 Example 3 CB5230 20 60 20
Composite Preparation Example 3 Example 4 CB5230 20 60 20
Composite Preparation Example 4 Example 5 CB5230 20 60 20
Composite Preparation Example 5 Example 3 CB5290 30 50 20
Composite Material Comparative Preparation Example 1 Comparative Example 1 CB5230 20 60 20
Composite Material Comparative Preparation Example 2 Comparative Example 2 CB5230 20 60 20
Composite Material Comparative Preparation Example 3 Comparative Example 3 CB5230 20 60 20
Composite Material Comparative Preparation Example 4 Comparative Example 5 CB5230 20 60 20
Composite Material Comparative Preparation Example 5 Comparative Example 6 CB5230 20 60 20
Composite Material Comparative Preparation Example 6 Comparative Example 7 CB5230 20 60 20
Composite Material Comparative Preparation Example 7 Comparative Example 5 CB5290 30 50 20
[247]
Experimental Example 2: Evaluation of physical properties of polypropylene-based composites
[248]
In order to confirm the physical properties of the polypropylene-based composites prepared in Composite Preparation Examples 1 to 5 and Composite Comparative Preparation Examples 1 to 7, the polypropylene-based composite was injection molded at a temperature of 230° C. using an injection molding machine to prepare a specimen After standing for 1 day in a constant temperature and humidity room, specific gravity of the polymer, melt index of the polymer, tensile strength, flexural strength and flexural modulus, low temperature and room temperature impact strength, and shrinkage were measured. The physical properties of the prepared specimens are shown in Table 5 below.
[249]
1) Specific gravity
[250]
Measured according to ASTM D792.
[251]
2) Polymer Melt Index (MI)
[252]
The melt index (MI) of the polymer was measured by ASTM D-1238 (Condition E, 230°C, 2.16 kg load).
[253]
3) Tensile strength, and flexural strength
[254]
Measurements were made according to ASTM D790 using an INSTRON 3365 instrument.
[255]
4) Low and room temperature impact strength
[256]
It was carried out according to ASTM D256, the impact strength was measured at room temperature under the conditions of room temperature (23 ℃), and the low temperature impact strength was measured after standing in a low temperature chamber (-30 ℃) for more than 12 hours.
[257]
[258]
[Table 5]
importance MI
(g/10min) tensile strength flexural strength Low-temperature impact strength room temperature impact strength
Composite Preparation Example 1 1.033 14.3 211 341 4.7 42.1
Composite Preparation Example 2 1.041 14.6 211 336 4.7 43.9
Composite Preparation Example 3 1.030 13.9 206 334 4.8 42.5
Composite Preparation Example 4 1.038 13.9 205 327 4.7 40.9
Composite Preparation Example 5 1.037 14.6 219 344 3.6 34.5
Composite Material Comparative Preparation Example 1 1.03 15.0 216 340 3.8 37.3
Composite Material Comparative Preparation Example 2 1.032 17.0 239 336 3.8 34.8
Composite Material Comparative Preparation Example 3 1.032 17.4 238 334 3.8 34.5
Composite Material Comparative Preparation Example 4 1.036 17.7 217 336 4.3 32.9
Composite Material Comparative Preparation Example 5 1.031 17.8 217 333 4.4 33.1
Composite Material Comparative Preparation Example 6 1.031 16.2 171 246 8.4 53.7
Composite Material Comparative Preparation Example 7 1.033 16.7 168 241 9.0 52.8
[259]
Referring to Table 5, when comparing the polypropylene-based composites including the olefin-based copolymer having the same level of density and MI value, the polypropylene-based composite prepared using the olefin-based polymer of Examples is the olefin-based composite of Comparative Example It can be seen that mechanical strength such as tensile strength and flexural strength is improved while maintaining similar levels of low-temperature impact strength and room-temperature impact strength compared to polypropylene-based composites manufactured using polymers. Through this, it was confirmed that when the olefin-based copolymer exhibiting high mechanical rigidity by introducing the high crystallinity region of Example is included in the polypropylene-based composite, the mechanical rigidity of the polypropylene-based composite can be increased.
Claims
[Claim 1]
Olefin-based polymers satisfying the requirements of (1) to (3) below: (1) Melt Index (MI, 190°C, 2.16 kg load condition) is 0.1 g/10 min to 10.0 g/10 min, (2 ) the density (d) is 0.860 g/cc to 0.880 g/cc, (3) T(90)-T(50)≤50 when measured by differential scanning calorimetry (SSA), and T(95)-T( 90)≥10, where T(50), T(90) and T(95) are respectively 50% and 90% when the temperature-heat capacity curve is fractionated from the differential scanning calorimetry precision measurement (SSA) measurement result, respectively. , and the temperature at which 95% melts.
[Claim 2]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer further satisfies (4) a weight average molecular weight (Mw) of 10,000 g/mol to 500,000 g/mol.
[Claim 3]
[Claim 2] The olefin-based polymer according to claim 1, wherein the olefin-based polymer further satisfies (5) a molecular weight distribution (MWD) of 0.1 to 6.0.
[Claim 4]
[Claim 2] The olefin-based polymer according to claim 1, wherein the olefin-based polymer further satisfies the requirement of (6) a melting point of 20°C to 70°C as measured by differential scanning calorimetry (DSC).
[Claim 5]
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 5.5 g/10 min.
[Claim 6]
The method according to claim 1, wherein the olefin-based polymer is 30≤T(90)-T(50)≤40, and 10≤T(95)-T(90)≤20 as measured by differential scanning calorimetry (SSA). Olefinic polymers.
[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]
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-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 9]
The olefin-based polymer according to claim 1, wherein the olefin-based polymer is a copolymer of ethylene and 1-butene.
[Claim 10]
a melt index (MI) of 0.4 g/10 min to 7.0 g/10 min; density (d) from 0.860 g/cc to 0.880 g/cc; When measuring differential scanning calorimetry (SSA), 20≤T(90)-T(50)≤45, and 10≤T(95)-T(90)≤30; a weight average molecular weight (Mw) of 10,000 to 500,000 g/mol; a molecular weight distribution (MWD) of 0.1 to 6.0; An olefin-based polymer having a melting point of 20°C to 60°C as measured by differential scanning calorimetry (DSC).
[Claim 11]
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; aryl amido; or an alkylidene radical having 1 to 20 carbon atoms.
[Claim 12]
According to claim 11, wherein the olefin-based polymer is prepared by a continuous solution polymerization reaction using a continuous stirred reactor (Continuous Stirred Tank Reactor) by adding hydrogen in the presence of the catalyst composition for olefin polymerization, the olefin-based polymer.
[Claim 13]
a melt index (MI) of 0.4 g/10 min to 7.0 g/10 min; density (d) from 0.860 g/cc to 0.880 g/cc; An olefin-based polymer satisfying the requirements of 30≤T(90)-T(50)≤40 and 10≤T(95)-T(90)≤20 when measured by differential scanning calorimetry (SSA), the olefin The olefin-based polymer is obtained 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 comprising a transition metal compound of Formula 1 below: [ Formula 1] In Formula 1, R 1 is the same as or different from each other, and each independently represents hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl, silyl, alkylaryl, arylalkyl, or hydrocarbyl. It is a metalloid radical of a Group 4 metal substituted with bil, 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; aryl amido; or an alkylidene radical having 1 to 20 carbon atoms.
[Claim 14]
The olefin-based polymer according to claim 13, wherein the amount of the hydrogen gas is 0.35 to 3 parts by weight based on 1 part by weight of the olefin-based monomer.