This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0052042 dated May 04, 2018, and all contents disclosed in the documents 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 copolymer and a method for producing the same, and more specifically, to a low-density olefin-based copolymer with improved physical properties such as hardness, flexural strength, and tensile strength while having high fluidity by controlling the content and type of unsaturated functional groups in the olefin-based copolymer. It relates to a copolymer and a method for preparing the same.
background
[5]
Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed according to their respective characteristics. Ziegler-Natta catalyst has been widely applied to existing commercial processes since its invention in the 1950s. There is a problem in that there is a limit in securing the desired physical properties because the composition distribution is not uniform.
[6]
On the other hand, the metallocene catalyst is composed of a combination of a main catalyst containing a transition metal compound as a main component and a cocatalyst containing an organometallic compound containing aluminum as a main component. Such a catalyst is a homogeneous complex catalyst and is a single site catalyst. The molecular weight distribution is narrow depending on the single active point characteristic, and a polymer with a uniform composition distribution of the comonomer is obtained. It has properties that can change crystallinity, etc.
[7]
U.S. Patent No. 5,914,289 discloses a method of controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount of solvent used in preparing the supported catalyst and preparation time are required. , the inconvenience of having to support each of the metallocene catalysts to be used on a carrier followed.
[8]
Korean Patent Application No. 10-2003-0012308 discloses a method of controlling molecular weight distribution by supporting a double-nuclear metallocene catalyst and a single-nuclear metallocene catalyst together with an activator on a carrier to change the combination of catalysts in the reactor and polymerization is starting However, this method has a limitation in simultaneously realizing the characteristics of each catalyst, and also has a disadvantage in that the metallocene catalyst portion is released from the carrier component of the finished catalyst, thereby causing fouling in the reactor.
[9]
On the other hand, linear low-density polyethylene is produced by copolymerizing ethylene and alpha-olefin at low pressure using a polymerization catalyst, and is a resin having a narrow molecular weight distribution, short-chain branches of a constant length, and no long-chain branches. The linear low-density polyethylene film has high breaking strength and elongation, along with the characteristics of general polyethylene, and excellent tensile strength and falling impact strength. Therefore, the use of stretch films and overlap films, which are difficult to apply to conventional low-density polyethylene or high-density polyethylene, is increasing. have.
[10]
However, most of the linear low-density polyethylene using 1-butene or 1-hexene as a comonomer is produced in a single gas phase reactor or a single loop slurry reactor, and the productivity is high compared to the process using 1-octene comonomer, but these products are also used Due to limitations in catalyst technology and process technology, the physical properties are significantly inferior to those in the case of using 1-octene comonomer, and the molecular weight distribution is narrow, resulting in poor processability.
[11]
In US Patent No. 4,935,474, two or more metallocene compounds are used to report a polyethylene production method having a broad molecular weight distribution. U.S. Patent No. 6,828,394 reports on a method for producing polyethylene, which has excellent processability and is particularly suitable for films, by using a mixture of those having good comonomer binding properties and those not having good comonomer binding properties. In addition, in U.S. Patent Nos. 6,841,631 and 6,894,128, polyethylene having a bicrystalline or polycrystalline molecular weight distribution is prepared with a metallocene-based catalyst using at least two metal compounds, and is used in films, blow molding, pipes, etc. reported to be applicable. However, these products have improved processability, but the dispersion state by molecular weight within the unit particles is not uniform, so the extrusion appearance is rough and the physical properties are not stable even under relatively good extrusion conditions.
[12]
Against this background, there is a constant demand for the production of better products with a balance between physical properties and processability, and in particular, the need for a polyethylene copolymer having excellent processability is further demanded.
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[13]
An object of the present invention is to provide a low-density olefin-based copolymer having improved physical properties such as hardness, flexural strength, and tensile strength while having high fluidity.
[14]
In addition, another object to be solved by the present invention is to provide a method for producing the olefin-based copolymer.
means of solving the problem
[15]
In order to solve the above problems, the present invention (1) the density (d) is 0.85 to 0.89 g / cc, (2) the melt index (Melt Index, MI, 190 ℃, 2.16 kg load condition) 15 g/10 min to 100 g/10 min, (3) the number of unsaturated functional groups per 1,000 carbon atoms (total V) is 0.8 or less, (4) vinylene, vinyl, and total V per 1,000 carbon atoms measured through nuclear magnetic spectroscopy It provides an olefin-based copolymer satisfying the following (a) and (b).
[16]
(a) vinylene/total V = 0.1 to 0.7
[17]
(b) vinylene/vinyl = 0.8 to 1.6
[18]
In addition, in order to solve the other problem, the present invention provides a step of polymerizing an olefinic monomer by adding hydrogen at a rate of 10 to 100cc/min in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of Formula 1 below. It provides a method for producing the olefin-based copolymer, including.
[19]
[Formula 1]
[20]

[21]
In Formula 1,
[22]
R 1 is hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms;
[23]
R 2a to R 2e are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; or aryl having 6 to 20 carbon atoms,
[24]
R 3 is hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 6 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkyl amido having 1 to 20 carbon atoms; aryl amido having 6 to 20 carbon atoms; alkylidene having 1 to 20 carbon atoms; or halogen, alkyl having 1 to 20 carbons, cycloalkyl having 3 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons, and aryl having 6 to 20 carbons substituted with one or more selected from the group consisting of is phenyl,
[25]
R 4 to R 9 are each independently hydrogen; silyl; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 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; arylalkyl having 7 to 20 carbon atoms; or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; Two or more adjacent to each other among R 6 to R 9 may be connected to each other to form a ring,
[26]
Q is Si, C, N, P or S;
[27]
M is a group 4 transition metal,
[28]
X 1 and X 2 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 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; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; arylamino having 6 to 20 carbon atoms; or an alkylidene having 1 to 20 carbon atoms.
Effects of the Invention
[29]
The olefin-based copolymer according to the present invention can exhibit improved physical properties in terms of hardness, flexural strength, tear strength, etc. while high fluidity by controlling the content and type of unsaturated functional groups in the olefin-based copolymer.
Best mode for carrying out the invention
[30]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[31]
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.
[32]
As used herein, the term "polymer" refers to a polymer compound prepared by polymerization of monomers of the same or different types. The generic term "polymer" includes the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer". Also, the term “interpolymer” refers to a polymer prepared by polymerization of two or more different types of monomers. The generic term "interpolymer" refers to the term "copolymer" (which is commonly used to refer to polymers prepared from two different monomers), as well as the term "copolymer" (usually used to refer to polymers prepared from three different types of monomers). used) the term "terpolymer". It includes polymers prepared by polymerization of four or more types of monomers.
[33]
[34]
The olefin-based copolymer according to the present invention satisfies the requirements of the following (1) to (4).
[35]
(1) the density (d) is 0.85 to 0.89 g / cc,
[36]
(2) the melt index (Melt Index, MI, 190 ℃, 2.16 kg load condition) is 15 g / 10 minutes to 100 g / 10 minutes,
[37]
(3) the number of unsaturated functional groups per 1,000 carbon atoms (total V) is 0.8 or less,
[38]
(4) Vinylene, vinyl, and total V per 1,000 carbon atoms measured through nuclear magnetic spectroscopy satisfy the following (a) and (b).
[39]
(a) vinylene/total V = 0.1 to 0.7
[40]
(b) vinylene/vinyl = 0.8 to 1.6
[41]
[42]
The olefinic copolymer according to the present invention exhibits a low density of 0.85 g/cc to 0.89 g/cc when measured according to ASTM D-792, specifically 0.855 to 0.89 g/cc, more specifically 0.86 to 0.89 g/cc density may be present. The olefinic copolymer according to the present invention exhibits a low density in the above range.
[43]
The melt index (MI) can be adjusted by adjusting the amount of the catalyst used in the process of polymerizing the olefin-based copolymer for the comonomer, and affects the mechanical properties and impact strength, and moldability of the olefin-based copolymer. . In the present specification, the melt index is measured at 190 ° C. and 2.16 kg load condition according to ASTM D1238 under a low density condition of 0.85 to 0.89 g/cc, and may be 15 g/10 min to 100 g/10 min, specifically 15 g/10 min to 80 g/10 min, more specifically 16 g/10 min to 70 g/10 min.
[44]
The olefin-based copolymer (3) the number of unsaturated functional groups per 1,000 carbon atoms (total V) is 0.8 or less, except when the number of unsaturated functional groups per 1,000 carbon atoms (total V) is 0. In addition, the number of unsaturated functional groups per 1,000 carbon atoms (total V) may be specifically 0.01 to 0.8, more specifically 0.15 to 0.7.
[45]
In addition, the olefinic copolymer satisfies (a) and (b) below in (4) vinylene, vinyl, and total V per 1,000 carbon atoms measured through nuclear magnetic spectroscopy.
[46]
(a) vinylene/total V = 0.1 to 0.7
[47]
(b) vinylene/vinyl = 0.8 to 1.6
[48]
(a) and (b) represent the ratio of vinylene and the ratio of vinylene and vinyl among the unsaturated functional groups, respectively.
[49]
The (a) vinylene/total V may be 0.1 to 0.7, specifically 0.2 to 0.6, more specifically 0.25 to 0.5.
[50]
In addition, (b) vinylene/vinyl may be 0.8 to 1.6, specifically 0.8 to 1.5, more specifically 0.9 to 1.4.
[51]
The olefin-based copolymer has a vinylene, vinyl, and unsaturated functional group per 1,000 carbon atoms (total V) that satisfies the conditions of (3) and (4), so the molecular weight distribution of the olefin-based copolymer may be reduced, In addition, when it has the same level of density and melt index compared to the conventional olefin-based copolymer, it can exhibit more improved tensile strength, elongation, and flexural modulus.
[52]
The olefin-based copolymer may have a vinyl content of less than 0.6 per 1000 carbon atoms in the copolymer. Specifically, the vinyl content may be 0.5 or less per 1000 carbon atoms constituting the copolymer, and more specifically, 0.3 or less.
[53]
Meanwhile, the olefin-based copolymer may have a vinylene content of less than 0.5 per 1000 carbon atoms in the copolymer. Specifically, the vinyl content may be 0.4 or less per 1000 carbon atoms constituting the copolymer, and more specifically, 0.3 or less.
[54]
The content of vinyl or vinylene in the copolymer is possible through control of the polymerization temperature and hydrogen input amount during manufacture. The olefin-based copolymer according to the present invention has a low vinyl and vinylene content as described above, so that the molecular weight distribution can be reduced. have.
[55]
In the present invention, the content of vinyl and vinylene in the copolymer may be calculated from the results of NMR analysis. Specifically, after dissolving the copolymer in TCE-d2 solvent, it was measured 2048 times at room temperature with a acquisition time of 3 seconds and a pulse angle of 30° using a Bruker AVANCEIII 500 MHz NMR equipment, and the comonomer content was measured in the range of 0.5 to 1.5 ppm. It is calculated using the integral value of the ethylene, 1-butene, and 1-octene peaks of 3790).
[56]
[57]
The olefinic copolymer according to an example of the present invention may further satisfy (5) a weight average molecular weight (Mw) of 10,000 g/mol to 80,000 g/mol, and the weight average molecular weight (Mw) is specifically 20,000 g/mol It may be mol to 70,000 g/mol, and more specifically, 30,000 g/mol to 65,000 g/mol.
[58]
In addition, the olefin-based copolymer 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 (6) molecular weight distribution (MWD; Molecular Weight Distribution) of 1.5 to 3.0 may be satisfied, and the molecular weight distribution (MWD) may be specifically 1.5 to 2.5, more specifically 1.9 to 2.15.
[59]
In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC).
[60]
In general, the density of the olefin-based copolymer is affected by the type and content of the monomer used during polymerization, the degree of polymerization, and the like. The olefinic copolymer of the present invention is copolymerized by adding hydrogen (H 2 ) to a catalyst composition containing a transition metal compound having a characteristic structure. , the hardness is increased compared to the conventional copolymer having the same density, and as a result, it can have properties such as more improved tear strength, elongation, and flexural modulus compared to the conventional copolymer.
[61]
In addition, the olefin-based copolymer according to the present invention can exhibit a narrow molecular weight distribution within the above range by controlling the molecular weight distribution by adding an optimal amount of hydrogen during the polymerization reaction for preparing the same.
[62]
[63]
The olefin-based copolymer may be an olefin-based monomer, specifically, a copolymer of two or more selected from 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. .
[64]
The alpha-olefin monomer 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-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, 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.
[65]
Specifically, the olefin-based copolymer may be a copolymer of ethylene and an alpha-olefin-based monomer having 3 to 12 carbon atoms, and specifically, may be a copolymer of ethylene and an alpha-olefin-based monomer having 3 to 10 carbon atoms.
[66]
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. have.
[67]
When the olefinic copolymer is a copolymer of ethylene and alpha-olefin, the amount of the alpha-olefin is 15 wt% to 45 wt%, specifically 20 wt% to 45 wt%, more specifically, based on the total weight of the copolymer. It may be 20% to 40% by weight.
[68]
When included in the above range, it is easy to implement the above-described physical properties,
[69]
In one example of the present invention, the olefin-based copolymer is a copolymer of ethylene and 1-octene, has a tensile elongation of 500% or more, measured according to ASTM D638 (50 mm/min), and a tear strength of 20 kgf/ cm 2 or more, and the flexural modulus (Secant 1%) measured according to ASTM D790 may be 10 kgf/cm 2 or more. Specifically, the olefin-based copolymer is a copolymer of ethylene and 1-octene, has a tensile elongation of 1,000% or more, measured according to ASTM D638 (50 mm/min), and a tear strength of 25 kgf/cm 2 to 40 kgf/cm 2 and may have a flexural modulus (Secant 1%) of 10.0 kgf/cm 2 to 30.0 kgf/cm 2 measured according to ASTM D790 .
[70]
In addition, in an example of the present invention, the olefin-based copolymer is a copolymer of ethylene and 1-butene, has a tensile elongation of 500% or more measured according to ASTM D638 (50 mm/min), and a tear strength of 20 kgf/cm 2 to 50 kgf/cm 2 , and a flexural modulus (Secant 1%) measured according to ASTM D790 may be 10.0 kgf/cm 2 or more. Specifically, the olefin-based copolymer is a copolymer of ethylene and 1-butene, has a tensile elongation of 500% to 1000% measured according to ASTM D638 (50 mm/min), and a tear strength of 20 kgf/cm 2 to 40 kgf/cm 2 , and the flexural modulus (Secant 1%) measured according to ASTM D790 may be 10.0 kgf/cm 2 to 30.0 kgf/cm 2 .
[71]
The olefinic copolymer according to an embodiment of the present invention having the above physical properties and structural characteristics, hydrogen is continuously added in the presence of a metallocene catalyst composition including one or more transition metal compounds in a single reactor, It may be prepared through a continuous solution polymerization reaction of polymerizing an olefinic monomer.
[72]
Accordingly, in the olefinic copolymer 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 copolymer according to the present invention does not contain a block copolymer, and from the group consisting of a random copolymer, an alternating copolymer, and a graft copolymer. may be selected, and more specifically, may be a random copolymer.
[73]
Specifically, the olefin-based copolymer of the present invention comprises a step of polymerizing the olefinic monomer by adding hydrogen at 10 to 100 cc/min in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of Formula 1 below It can be obtained by a manufacturing method.
[74]
However, in the preparation of the olefin-based copolymer according to an embodiment of the present invention, the scope of the structure of the following transition metal compound is not limited to a specific disclosed form, and all changes and equivalents included in the spirit and technical scope of the present invention or substitutes.
[75]
[Formula 1]
[76]

[77]
In Formula 1,
[78]
R 1 is hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms;
[79]
R 2a to R 2e are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; or aryl having 6 to 20 carbon atoms,
[80]
R 3 is hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 6 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkyl amido having 1 to 20 carbon atoms; aryl amido having 6 to 20 carbon atoms; alkylidene having 1 to 20 carbon atoms; or halogen, alkyl having 1 to 20 carbons, cycloalkyl having 3 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons, and aryl having 6 to 20 carbons substituted with one or more selected from the group consisting of is phenyl,
[81]
R 4 to R 9 are each independently hydrogen; silyl; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 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; arylalkyl having 7 to 20 carbon atoms; or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; Two or more adjacent to each other among R 6 to R 9 may be connected to each other to form a ring,
[82]
Q is Si, C, N, P or S;
[83]
M is a group 4 transition metal,
[84]
X 1 and X 2 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 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; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; arylamino having 6 to 20 carbon atoms; or an alkylidene having 1 to 20 carbon atoms.
[85]
[86]
In an example of the present invention, in the transition metal compound of Formula 1,
[87]
wherein R 1 is hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms,
[88]
The R 2a to R 2e are each independently hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; alkoxy having 1 to 12 carbon atoms; or phenyl,
[89]
wherein R 3 is hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 13 carbon atoms; arylalkyl having 7 to 13 carbon atoms; Or it may be phenyl substituted with one or more selected from the group consisting of halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, and phenyl,
[90]
The R 4 to R 9 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 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,
[91]
two or more adjacent to each other among R 6 to R 9 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 12 carbon atoms, or aryl having 6 to 12 carbon atoms,
[92]
Q may be Si,
[93]
M may be Ti,
[94]
The X 1 and X 2 are each independently hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; aryl having 6 to 12 carbon atoms; alkylaryl having 7 to 13 carbon atoms; arylalkyl having 7 to 13 carbon atoms; alkylamino having 1 to 13 carbon atoms; arylamino having 6 to 12 carbon atoms; Or it may be an alkylidene having 1 to 12 carbon atoms.
[95]
[96]
In addition, in another example of the present invention, in the transition metal compound of Formula 1,
[97]
wherein R 1 is hydrogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkoxy having 1 to 12 carbon atoms; aryl having 6 to 12 carbon atoms; arylalkoxy having 7 to 13 carbon atoms; alkylaryl having 7 to 13 carbon atoms; Or it may be an arylalkyl having 7 to 13 carbon atoms,
[98]
The R 2a to R 2e are each independently hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; alkoxy having 1 to 12 carbon atoms; or phenyl,
[99]
wherein R 3 is hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; alkylaryl having 7 to 13 carbon atoms; arylalkyl having 7 to 13 carbon atoms; phenyl; Or it may be phenyl substituted with one or more selected from the group consisting of halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, and phenyl,
[100]
The R 4 to R 9 are each independently hydrogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; aryl having 6 to 12 carbon atoms; alkylaryl having 7 to 13 carbon atoms; Or it may be an arylalkyl having 7 to 13 carbon atoms,
[101]
two or more adjacent to each other among R 6 to R 9 may be connected to each other to form an aliphatic ring having 5 to 12 carbon atoms or an aromatic ring having 6 to 12 carbon atoms;
[102]
The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or aryl having 6 to 12 carbon atoms,
[103]
Q may be Si,
[104]
M may be Ti,
[105]
The X 1 and X 2 are each independently hydrogen; halogen; an alkyl group having 1 to 12 carbon atoms; Or it may be alkenyl having 2 to 12 carbon atoms.
[106]
[107]
In addition, in another example of the present invention, in the transition metal compound of Formula 1,
[108]
Wherein R 1 may be hydrogen or alkyl having 1 to 12 carbon atoms,
[109]
The R 2a to R 2e are each independently hydrogen; alkyl having 1 to 12 carbon atoms; Or it may be an alkoxy having 1 to 12 carbon atoms,
[110]
wherein R 3 is hydrogen; alkyl having 1 to 12 carbon atoms; or phenyl,
[111]
The R 4 and R 5 are each independently hydrogen; Or it may be an alkyl having 1 to 12 carbon atoms,
[112]
The R 6 to R 9 may each independently be hydrogen or methyl,
[113]
Q may be Si,
[114]
M may be Ti,
[115]
The X 1 and X 2 may each independently be hydrogen or an alkyl having 1 to 12 carbon atoms.
[116]
[117]
The compound represented by Formula 1 may be any one of compounds represented by Formulas 1-1 to 1-10 below.
[118]
[Formula 1-1]
[119]

[120]
[Formula 1-2]
[121]

[122]
[Formula 1-3]
[123]

[124]
[Formula 1-4]
[125]

[126]
[Formula 1-5]
[127]

[128]
[Formula 1-6]
[129]

[130]
[Formula 1-7]
[131]

[132]
[Formula 1-8]
[133]

[134]
[Formula 1-9]
[135]

[136]
[Formula 1-10]
[137]

[138]
[139]
In addition, it may be a compound having various structures within the range defined in Formula 1 above.
[140]
In the transition metal compound represented by Formula 1, the metal site is connected by a cyclopentadienyl ligand into which tetrahydroquinoline is introduced, and thus the Cp-MN angle is structurally narrow, and the Q 3 -MQ 4 angle that the monomer approaches is wide. features to retain. 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 can be obtained even at high polymerization temperatures. It is possible to polymerize the olefinic copolymer having.
[141]
Each of the substituents defined in the present specification will be described in detail as follows.
[142]
As used herein, the term 'hydrocarbyl group' is, unless otherwise stated, the number of carbon atoms consisting only of carbon and hydrogen, regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl or arylalkyl. It means a monovalent hydrocarbon group of 1-20.
[143]
As used herein, the term 'halogen' means fluorine, chlorine, bromine or iodine, unless otherwise noted.
[144]
The term 'alkyl' as used herein, unless otherwise stated, refers to a straight-chain or branched hydrocarbon residue.
[145]
As used herein, the term 'alkenyl' refers to a straight-chain or branched alkenyl group, unless otherwise specified.
[146]
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.
[147]
According to an example of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.
[148]
The alkylaryl group means an aryl group substituted by the alkyl group.
[149]
The arylalkyl group means an alkyl group substituted by the aryl group.
[150]
The ring (or heterocyclic group) refers to 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.
[151]
The alkyl amino group refers to an amino group substituted by the alkyl group, and includes, but is not limited to, a dimethylamino group, a diethylamino group, and the like.
[152]
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. no.
[153]
The transition metal compound of Formula 1 has a density of 0.89 g/cc or less, more specifically, a density of 0.85 to 0.89 g/cc level, because a large amount of alpha-olefin as well as low-density polyethylene can be introduced due to the structural characteristics of the catalyst. The preparation of low density polyolefin copolymers is possible.
[154]
[155]
The transition metal compound of Formula 1 may be used alone or in the form of a composition further comprising one or more of the promoter compounds represented by Formula 2, Formula 3, and Formula 4 in addition to the transition metal compound of Formula 1, polymerization reaction can be used as a catalyst for The cocatalyst compound may help to activate the transition metal compound of Formula 1 above.
[156]
[Formula 2]
[157]
-[Al(R 10 )-O] a -
[158]
[Formula 3]
[159]
A(R 10 ) 3
[160]
[Formula 4]
[161]
[LH] + [W(D) 4 ] - or [L] + [W(D) 4 ] -
[162]
In Formulas 2 to 4,
[163]
R 10 may be the same as or different from each other, and are each independently selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
[164]
A is aluminum or boron,
[165]
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,
[166]
H is a hydrogen atom,
[167]
L is a neutral or cationic Lewis acid,
[168]
W is a group 13 element,
[169]
a is an integer greater than or equal to 2;
[170]
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).
[171]
Examples of the compound represented by Formula 3 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, and tricyclopentylaluminum. , tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and specifically may be selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.
[172]
Examples of the compound represented by Formula 4 include triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, trimethylammoniumtetra (o,p-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetrapentafluorophenylboron, N,N -diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtetraphenylboron, dimethyl Anilinium tetrakis(pentafluorophenyl)borate, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra(p-tolyl)aluminum, trimethylammoniumtetra(p-tolyl)aluminum Propylammoniumtetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammoniumtetra(p-trifluoromethylphenyl)aluminum, trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum , tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, diethylammoniumtetrapentatenttraphenylaluminum, triphenyl Phosphonium tetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, triphenylcarboniumtetra(p-trifluoromethylphenyl) ) boron or triphenylcarboniumtetrapentafluorophenylboron.
[173]
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.
[174]
In addition, the catalyst composition may be prepared by contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 2 as a second method.
[175]
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 to the compound represented by Formula 2 or Formula 3 may be 1/5,000 to 1/2, and specifically may be 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 in 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, so the activity of the catalyst composition produced may fall, and if the molar ratio is less than 1/25, the metal compound is completely 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.
[176]
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/Compound represented by Formula 2 may be 1/10,000 to 1/10, and specifically 1/5,000 to 1/100, and more specifically, may be from 1/300 to 1/500. When the molar ratio exceeds 1/10, the amount of the activator is relatively small, so the activation of the metal compound may not be completely achieved, and thus the activity of the resulting catalyst composition may decrease. If the molar ratio is less than 1/10,000, the activation of the metal compound is completely achieved, but the cost of the catalyst composition may not be economical or the purity of the resulting polymer may be deteriorated with the excess amount of activator remaining.
[177]
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.
[178]
In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a supported form on a carrier.
[179]
The carrier may be used without any particular limitation as long as it is used as a carrier in a metallocene-based catalyst. Specifically, the carrier may be silica, silica-alumina or silica-magnesia, and any one or a mixture of two or more thereof may be used.
[180]
Among them, when the carrier is silica, since the functional group of the silica carrier and the metallocene compound of Formula 1 chemically forms a bond, there is almost no catalyst released from the surface during the olefin polymerization process. As a result, during the manufacturing process of the olefin-based copolymer, it is possible to prevent the occurrence of fouling caused by agglomeration of the reactor wall surface or the polymer particles. In addition, the olefin-based copolymer prepared in the presence of the catalyst including the silica carrier is excellent in particle shape and apparent density of the polymer.
[181]
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.
[182]
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 .
[183]
The drying temperature of the carrier is preferably 200 to 800°C, more preferably 300 to 600°C, and most preferably 300 to 400°C. When the drying temperature of the carrier is less than 200 ℃, there is too much moisture and the surface moisture and the cocatalyst react. It is undesirable because it disappears and only the siloxane remains, reducing the reaction site with the promoter.
[184]
In addition, the amount of hydroxyl groups on the surface of the carrier is preferably 0.1 to 10 mmol/g, more preferably 0.5 to 5 mmol/g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions or drying conditions of the carrier, such as temperature, time, vacuum or spray drying, and the like.
[185]
On the other hand, the polymerization reaction of the olefin-based copolymer may be performed by continuously adding hydrogen in the presence of the catalyst composition and continuously polymerizing the olefin-based monomer.
[186]
The polymerization reaction of the olefin monomer may be performed under an inert solvent, and the inert solvent includes benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, but not limited thereto.
[187]
[188]
The polymerization of the olefin-based copolymer may be performed through a reaction at a temperature of about 25 to about 500° C. and a pressure of about 1 to about 100 kgf/cm 2 .
[189]
Specifically, the polymerization of the olefin-based copolymer may be carried out at a temperature of about 25 to about 500 °C, specifically 80 to 250 °C, more preferably at a temperature of 100 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
[190]
[191]
The olefin-based copolymer of the present invention may be usefully used in the manufacture of a molded article.
[192]
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.
[193]
Modes for carrying out the invention
[194]
Example
[195]
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.
[196]
[197]
Preparation Example 1: Preparation of transition metal compound 1
[198]
[Preparation of ligand compound]
[199]

[200]

[201]
Preparation of chloro- 1-(1,2-dimethyl-3H- benzo[b]cyclopenta[d]thiophen- 3-yl)-1,1-( methyl )(phenyl)silane
[202]
In a 250 ml Schlenk flask, put 10 g (1.0 eq, 49.925 mmol) of 1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophene and 100 ml of THF, and 22 ml of n-BuLi (1.1 eq, 54.918 mmol, 2.5 M in hexane) was added dropwise at -30°C, followed by stirring at room temperature for 3 hours. The stirred Li-complex THF solution was cannulated at -78°C in a Schlenk flask containing 8.1 ml (1.0 eq, 49.925 mmol) of dichloro(methyl)(phenyl)silane and 70 ml of THF, followed by stirring at room temperature overnight. After stirring, the mixture was dried in vacuo, and extracted with 100 ml of hexane.
[203]
[204]
[Preparation of transition metal compound]
[205]
Preparation of N- tert -butyl-1-(1,2-dimethyl-3H- benzo[b]cyclopenta[d]thiophen- 3-yl)-1,1-( methyl )(phenyl)silanamine
[206]
t-BuNH in 100 ml of extracted chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl)silane hexane solution 2 42 ml (8 eq, 399.4 mmol) was added at room temperature, followed by stirring at room temperature overnight. After stirring, the mixture was dried in vacuo, and extracted with 150 ml of hexane. After solvent drying, 13.36 g (68 %, dr = 1:1) of a yellow solid was obtained.
[207]
1 H NMR (CDCl 3 , 500 MHz): δ 7.93 (t, 2H), 7.79 (d,1H), 7.71 (d,1H), 7.60 (d, 2H), 7.48 (d, 2H), 7.40-7.10 (m, 10H, aromatic), 3.62 (s, 1H), 3.60 (s, 1H), 2.28 (s, 6H), 2.09 (s, 3H), 1.76 (s, 3H), 1.12 (s, 18H), 0.23 (s, 3H), 0.13 (s, 3H)
[208]

[209]
In a 100 ml Schlenk flask, put 4.93 g (12.575 mmol, 1.0 eq) of the ligand compound of Formula 2-4 and 50 ml (0.2M) of toluene, and 10.3 ml (25.779 mmol, 2.05 eq, 2.5M in hexane) of n-BuLi. was added dropwise at -30°C, followed by stirring at room temperature overnight. After stirring, 12.6 ml (37.725 mmol, 3.0 eq, 3.0 M in diethyl ether) of MeMgBr was added dropwise, and then TiCl 4 13.2 ml (13.204 mmol, 1.05 eq, 1.0 M in toluene) was added in order and stirred at room temperature overnight. . After stirring, the mixture was vacuum dried, extracted with 150 ml of hexane, and the solvent was removed to 50 ml, and then 4 ml (37.725 mmol, 3.0eq) of DME was added dropwise, followed by stirring at room temperature overnight. After vacuum drying again, the mixture was extracted with 150 ml of hexane. After solvent drying, 2.23 g (38 %, dr = 1:0.5) of a brown solid was obtained.
[210]
1 H NMR (CDCl 3 , 500 MHz): δ 7.98 (d, 1H), 7.94 (d, 1H), 7.71 (t, 6H), 7.50-7.30 (10H), 2.66 (s, 3H), 2.61 (s) , 3H), 2.15 (s, 3H), 1.62 (s, 9H), 1.56 (s, 9H), 1.53 (s, 3H), 0.93 (s, 3H), 0.31 (s, 3H), 0.58 (s, 3H), 0.51 (s, 3H), -0.26 (s, 3H), -0.39 (s, 3H)
[211]
[212]
Preparation Example 2: Preparation of transition metal compound 2
[213]
[Preparation of ligand compound]
[214]

[215]
In a 100 mL Schlenk flask, quantify 4.65 g (15.88 mmol) of chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-dimethylsilane After addition, 80 mL of THF was added thereto. After adding tBuNH 2 (4eq, 6.68 mL) at room temperature, the reaction was conducted at room temperature for 3 days. After the reaction, THF was removed and then filtered with hexane. After solvent drying, a yellow liquid was obtained in a yield of 4.50 g (86%).
[216]
1 H-NMR (in CDCl 3 , 500 MHz): 7.99 (d, 1H), 7.83 (d, 1H), 7.35 (dd, 1H), 7.24 (dd, 1H), 3.49 (s, 1H), 2.37 ( s, 3H), 2.17(s, 3H), 1.27(s, 9H), 0.19(s, 3H), -0.17(s, 3H).
[217]
[218]
[Preparation of transition metal compound]
[219]

[220]
N-tert-butyl-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-dimethylsilane prepared above in a 50 mL Schlenk flask An amine (1.06g, 3.22mmol/1.0eq) and 16.0 mL (0.2 M) of MTBE were added and stirred first. At -40°C, n-BuLi (2.64 mL, 6.60 mmol/2.05eq, 2.5 M in THF) was added, and the reaction was carried out at room temperature overnight. Thereafter, MeMgBr (2.68 mL, 8.05 mmol/2.5eq, 3.0 M in diethyl ether) was slowly added dropwise at -40°C, and then TiCl4 (2.68 mL, 3.22 mmol/1.0eq, 1.0 M in toluene) was added in this order. and reacted overnight at room temperature. Then, the reaction mixture was filtered through Celite using hexane. After solvent drying, a brown solid was obtained in a yield of 1.07 g (82%).
[221]
1 H-NMR (in CDCl 3 , 500 MHz): 7.99 (d, 1H), 7.68 (d, 1H), 7.40 (dd, 1H), 7.30 (dd, 1H), 3.22 (s, 1H), 2.67 ( s, 3H), 2.05 (s, 3H), 1.54 (s, 9H), 0.58 (s, 3H), 0.57 (s, 3H), 0.40 (s, 3H), -0.45 (s, 3H).
[222]
[223]
Example 1
[224]
After the 1.5L autoclave continuous process reactor was charged with hexane solvent (5 kg/h) and 1-octene (2 kg/h), the temperature at the top of the reactor was preheated to 136° C. Triisobutylaluminum compound (0.05 mmol/min) ), the transition metal compound (0.45 μmol/min) obtained in Preparation Example 1, and dimethylanilinium tetrakis(pentafluorophenyl) borate cocatalyst (1.35 μmol/min) were simultaneously introduced into the reactor as a catalyst. Ethylene (0.87 kg/h) hydrogen gas (28 cc/min) was introduced into the autoclave reactor and maintained at 136° 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 for more than 12 hours, the physical properties were measured.
[225]
[226]
Examples 2 to 8
[227]
As shown in Table 1 below, a copolymer was prepared in the same manner as in Example 1, except that the content of each material was changed.
[228]
[229]
Comparative Examples 1 to 7
[230]
As Comparative Example 1, Solumer 8730L (manufactured by SK Innovation) was purchased and used, as Comparative Example 3, DF7350 (manufactured by Mitsui) was purchased and used, and as Comparative Example 4, LC875 (manufactured by LG Chem) was purchased and used.
[231]
Comparative Examples 2, 5 and 6 were performed in the same manner as in Example 1, except that the transition metal compound obtained in Preparation Example 2 was used as a catalyst and the content of each material was changed as shown in Table 1 below. A copolymer was prepared.
[232]
Comparative Example 7 was the same as in Example 1, except that the transition metal compound obtained in Preparation Example 1 was used as a catalyst, hydrogen gas was not added as shown in Table 1, and the content of each material was different. A copolymer was prepared by the method of
[233]
[234]
[Table 1]
Catalyst (μmol/min) Cocatalyst (μmol/min) TiBAl (mmol/min) Ethylene (kg/h) Hydrogen (cc/min) Alpha Olefin Monomer Reaction temperature (℃)
1-octene (kg/h) 1-butene (kg/h)
Example 1 0.45 1.35 0.05 0.87 28 2.00 - 136
Example 2 0.60 1.80 0.05 0.87 20 2.00 - 150
Example 3 0.60 1.80 0.05 0.87 35 2.00 - 149
Example 4 0.25 0.75 0.05 0.87 30 - 0.80 135
Example 5 0.27 0.81 0.05 0.87 34 - 0.90 135
Example 6 0.38 1.14 0.05 0.87 19 - 0.91 151
Example 7 0.25 0.75 0.05 0.87 45 - 0.90 135
Example 8 0.40 2.40 0.05 0.87 30 - 1.00 150
Comparative Example 2 0.70 2.10 0.05 0.87 0 2.20 - 150
Comparative Example 5 0.37 1.11 0.05 0.87 0 - 1.00 150
Comparative Example 6 0.38 1.14 0.05 0.87 0 - 1.00 151
Comparative Example 7 0.40 2.40 0.05 0.87 0 - 1.00 151
[235]
Experimental Example 1
[236]
The copolymers of Examples 1 to 8 and Comparative Examples 1 to 7 were evaluated for physical properties according to the following method, and are shown in Table 2 below.
[237]
1) Density of the polymer
[238]
Measured by ASTM D-792.
[239]
2) Melt Index (MI) of the polymer
[240]
It was measured by ASTM D-1238 (Condition E, 190°C, 2.16 kg load).
[241]
3) Weight average molecular weight (g/mol) and molecular weight distribution (MWD)
[242]
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.
[243]
- Column: PL Olexis
[244]
- Solvent: TCB (Trichlorobenzene)
[245]
- Flow rate: 1.0 ml/min
[246]
- Sample concentration: 1.0 mg/ml
[247]
- Injection volume: 200 μl
[248]
- Column temperature: 160℃
[249]
- Detector: Agilent High Temperature RI detector
[250]
- Standard: Polystyrene (corrected by cubic function)
[251]
[Table 2]
Density (g/mL) MI (g/10min) Mw MWD %[1-C8](wt%) %[1-C4](wt%)
Example 1 0.869 33.7 46,000 2.05 35.8 0
Example 2 0.873 17.0 55,000 1.99 34.6 0
Example 3 0.874 45.0 42,000 1.98 33.9 0
Example 4 0.875 20.0 53,000 2.03 0 25.2
Example 5 0.871 32.4 47,000 2.01 0 27.0
Example 6 0.868 34.3 46,000 2.00 0 27.9
Example 7 0.872 62.0 32,000 2.02 0 27.6
Example 8 0.865 58.2 35,000 2.04 0 30.0
Comparative Example 1 0.869 29.2 48,000 2.34 37.9 0
Comparative Example 2 0.870 33.4 46,000 2.30 36.1 0
Comparative Example 3 0.870 29.5 48,000 1.93 0 26.8
Comparative Example 4 0.869 30.0 47,000 2.33 0 28.8
Comparative Example 5 0.870 30.3 47,000 2.16 0 28.2
Comparative Example 6 0.870 34.0 46,000 2.35 0 28.8
Comparative Example 7 0.864 5.4 69,000 2.18 0 29.1
[252]
Experimental Example 2
[253]
For the copolymers of Examples 1 to 8 and Comparative Examples 1 to 4, the number of vinylene, vinyl, vinylidene, and total unsaturated functional groups per 1,000 carbon atoms was measured according to the following method, and is shown in Table 3 below.
[254]
First, in order to remove residual 1-octene or 1-butene that may be present in the specimen, the polymer was prepared by re-precipitation before NMR analysis. Specifically, 1 g of the polymer was completely dissolved in chloroform at 70° C., and the resulting polymer solution was slowly poured into 300 ml of methanol with stirring to reprecipitate the polymer, and then the reprecipitated polymer was vacuum dried at room temperature. The above process was repeated once more to obtain a polymer from which residual 1-octene or 1-butene was removed.
[255]
A 50 mg specimen of the polymer obtained above was dissolved in 1 ml of TCE-d2 solvent. Using the Bruker AVANCEⅢ 500MHz NMR equipment, 2048 measurements were made at room temperature with an acquisition time of 3 seconds and a pulse angle of 30°. The comonomer content was calculated using the integral value of the ethylene, 1-butene, and 1-octene peaks in the range of 0.5 to 1.5 ppm. The number of double bonds was calculated based on the integral value of the double bonds in the 4.5-6.0 ppm region. Macromolecules 2014, 47, 3782-3790.
[256]
[Table 3]
vinylene trisubstituted alkenes vinyl vinylidene Total V Vinylene/Total V vinylene/vinyl
Example 1 0.08 0.04 0.08 0.07 0.25 0.320 1.000
Example 2 0.09 0.03 0.07 0.06 0.25 0.360 1.286
Example 3 0.05 0.02 0.05 0.04 0.16 0.313 1.000
Example 4 0.07 0.02 0.06 0.02 0.17 0.412 1.167
Example 5 0.18 0.07 0.19 0.2 0.63 0.286 0.947
Example 6 0.15 0.03 0.11 0.1 0.39 0.385 1.364
Example 7 0.12 0.02 0.13 0.09 0.36 0.333 0.923
Example 8 0.22 0.09 0.17 0.13 0.61 0.361 1.294
Comparative Example 1 0.06 0.02 0.12 0.03 0.23 0.261 0.500
Comparative Example 2 0.41 0.13 0.19 0.24 0.97 0.423 2.158
Comparative Example 3 0.10 0.02 0.04 0.05 0.2 0.500 2.500
Comparative Example 4 0.53 0.09 0.13 0.03 0.78 0.679 4.077
Comparative Example 5 0.62 0.09 0.29 0.35 1.35 0.459 2.138
Comparative Example 6 0.38 0.07 0.18 0.22 0.85 0.447 2.111
Comparative Example 7 0.07 0.07 0.18 0.15 0.77 0.091 0.389
[257]
Experimental Example 3
[258]
In addition, the tensile strength, elongation, and flexural modulus of the olefinic copolymers of Examples 1, 5, 7 and Comparative Examples 1 to 6 were measured according to the following method, and are shown in Table 4 below.
[259]
1) Polymer tensile strength and elongation
[260]
The olefinic copolymers of Examples 1, 5, 7 and Comparative Examples 1 to 6 were each extruded to prepare pellets, and then the tensile strength and tensile elongation at breakage were measured according to ASTM D638 (50 mm/min). .
[261]
2) flexural modulus of the polymer
[262]
The flexural modulus (Secant 1%) was measured according to ASTM D790.
[263]
[Table 4]
Types of comonomers Density (g/mL) MI (g/10min) Tensile strength (kgf/cm 2) Elongation (%) Flexural modulus (Secant 1%) (kgf/cm 2 )
Example 1 1-octene 0.869 33.7 33.5 1,000 or more 12.0
Comparative Example 1 1-octene 0.869 29.2 32.6 1,000 or more 10.9
Comparative Example 2 1-octene 0.870 33.4 29.1 1,000 or more 10.5
Example 5 1-butene 0.871 32.4 26.7 700 16.2
Example 7 1-butene 0.868 34.3 28.6 550 15.7
Comparative Example 3 1-butene 0.870 29.5 25.6 500 15.6
Comparative Example 4 1-butene 0.869 30.0 21.3 700 12.3
Comparative Example 5 1-butene 0.870 30.3 23.8 600 14.9
Comparative Example 6 1-butene 0.870 34.0 27.5 436 14.5
[264]
The olefin-based copolymer according to the present invention is a low-density olefin-based copolymer and may exhibit increased tear strength, elongation and flexural modulus at a density and melt index equivalent to that of a conventional olefin-based copolymer. Specifically, in Table 3 above, when the olefin-based copolymers prepared using the same comonomer (alpha-olefin monomer) and exhibiting the same density and MI are compared with each other, the olefin-based copolymer of Examples is per 1,000 carbon atoms. The number of unsaturated functional groups (total V) is 0.8 or less, and the vinylene, vinyl, and total V per 1,000 carbon atoms measured through nuclear magnetic spectroscopy satisfy all of the following (a) and (b), while the olefinic air of Comparative Example It can be seen that the coalescence does not satisfy this.
[265]
(a) vinylene/total V = 0.1 to 0.7
[266]
(b) vinylene/vinyl = 0.8 to 1.6
[267]
As a result, it can be confirmed that the olefin-based copolymer of Examples exhibits higher tear strength and flexural modulus with equal or superior elongation compared to the olefin-based copolymer of Comparative Examples. For example, the olefin-based copolymer of Example 1 exhibits higher tear strength and flexural modulus than the olefin-based copolymers of Comparative Examples 1 and 2, and also the molecular weight distribution (MWD) of the olefinic copolymer of Example 1 The coalescence shows a smaller value than the olefinic copolymers of Comparative Examples 1 and 2. In addition, the olefin-based copolymer of Example 5 exhibits higher tear strength and flexural modulus than the olefin-based copolymers of Comparative Examples 4 to 5. In addition, when the olefin-based copolymer of Example 7 is compared with the olefin-based copolymer of Comparative Example 6, it can be confirmed that it has better elongation, tear strength, and flexural strength.
[268]
Through these experiments, the olefin-based copolymer according to the present invention has a number of unsaturated functional groups per 1,000 carbon atoms (total V) of 0.8 or less, and vinylene, vinyl, and total V per 1,000 carbon atoms measured through nuclear magnetic spectroscopy. satisfies all of the above (a) and (b), so it was confirmed that it exhibited higher tear strength, elongation and flexural modulus compared to conventional olefin-based copolymers such as Comparative Examples 1, 3 and 4 .
[269]
In particular, the olefin-based copolymers of Example 8 and Comparative Example 7 showed differences in physical properties depending on whether hydrogen was added even when the same content of each material was used in the presence of the same catalyst composition. Specifically, Comparative Example 7 The olefinic copolymer shows a low MI, and the values ​​of vinylene/total V and vinylene/vinyl calculated from vinylene, vinyl, and total V values ​​per 1,000 carbon atoms measured through nuclear magnetic spectroscopy are 0.091 and 0.389, respectively. did not satisfy the above (a) and (b).
[270]
That is, the olefin-based copolymer according to the present invention is prepared by polymerizing the olefin-based monomer by adding hydrogen at 10 to 100 cc/min in the presence of a catalyst composition for olefin polymerization including the transition metal compound of Formula 1, Hydrogen controls the number of unsaturated functional groups in the olefinic copolymer to satisfy both the content ratios of (a) vinylene/total V and (b) vinylene/vinyl, but the olefinic copolymers of Comparative Examples 2 and 5 to 7 The coalescer could not satisfy the content ratio of (b) vinylene/vinyl. Accordingly, the olefin-based copolymer according to an embodiment of the present invention could exhibit superior properties in tensile strength, flexural modulus and elongation.
Claims
[Claim 1]
(1) the density (d) is 0.85 to 0.89 g / cc, (2) the melt index (Melt Index, MI, 190 ℃, 2.16 kg load condition) 15 g / 10 min to 100 g / 10 min, (3) ) The number of unsaturated functional groups per 1,000 carbon atoms (total V) is 0.8 or less, (4) The vinylene, vinyl, and total V per 1,000 carbon atoms measured through nuclear magnetic spectroscopy satisfy (a) and (b) below which is an olefin-based copolymer. (a) vinylene/total V = 0.1 to 0.7 (b) vinylene/vinyl = 0.8 to 1.6
[Claim 2]
The olefin-based copolymer according to claim 1, wherein the olefin-based copolymer further has (5) a weight average molecular weight (Mw) of 10,000 g/mol to 80,000 g/mol.
[Claim 3]
The olefin-based copolymer according to claim 1, wherein the olefin-based copolymer further has (6) a molecular weight distribution (MWD) of 1.5 to 3.0.
[Claim 4]
According to claim 1, wherein the olefin-based copolymer (3) the number of unsaturated functional groups per 1,000 carbon atoms (total V) is 0.15 to 0.7, the olefin-based copolymer.
[Claim 5]
According to claim 1, wherein the olefinic copolymer (4) vinylene, vinyl, total V per 1,000 carbon atoms measured through nuclear magnetic spectroscopy satisfies the following (a) and (b), olefinic copolymer coalescence. (a) vinylene/total V = 0.2 to 0.6 (b) vinylene/vinyl = 0.8 to 1.5
[Claim 6]
The olefin-based copolymer according to claim 1, wherein the olefin-based copolymer is a copolymer of ethylene and an alpha-olefin comonomer having 3 to 12 carbon atoms.
[Claim 7]
7. The method of claim 6, 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. Sen, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4 -Olefin comprising any one or a mixture of two or more selected from the group consisting of butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene based copolymer.
[Claim 8]
In the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of Formula 1, hydrogen is added at a rate of 10 to 100 cc/min to polymerize the olefinic monomer. : [Formula 1] In Formula 1, R 1 is hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms, and R 2a to R 2e are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; or aryl having 6 to 20 carbon atoms, and R 3is hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 6 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkyl amido having 1 to 20 carbon atoms; aryl amido having 6 to 20 carbon atoms; alkylidene having 1 to 20 carbon atoms; or halogen, alkyl having 1 to 20 carbons, cycloalkyl having 3 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons, and aryl having 6 to 20 carbons substituted with one or more selected from the group consisting of phenyl, and R 4 to R 9 are each independently hydrogen; silyl; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 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; arylalkyl having 7 to 20 carbon atoms; or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; At least two adjacent to each other of R 6 to R 9 may be connected to each other to form a ring, Q is Si, C, N, P or S, M is a Group 4 transition metal, X 1 and X 2are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 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; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; arylamino having 6 to 20 carbon atoms; or an alkylidene having 1 to 20 carbon atoms.
[Claim 9]
The method of claim 8, wherein R 1 is hydrogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkoxy having 1 to 12 carbon atoms; aryl having 6 to 12 carbon atoms; arylalkoxy having 7 to 13 carbon atoms; alkylaryl having 7 to 13 carbon atoms; or arylalkyl having 7 to 13 carbon atoms, wherein R 2a to R 2e are each independently hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; alkoxy having 1 to 12 carbon atoms; or phenyl, wherein R 3 is hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; alkylaryl having 7 to 13 carbon atoms; arylalkyl having 7 to 13 carbon atoms; phenyl; or phenyl substituted with one or more selected from the group consisting of halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, and phenyl, wherein R 4 to R 9 are each independently hydrogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; aryl having 6 to 12 carbon atoms; alkylaryl having 7 to 13 carbon atoms; or arylalkyl having 7 to 13 carbon atoms, and R 2 or more of 6 to R 9 may be connected to each other to form an aliphatic ring having 5 to 12 carbon atoms or an aromatic ring having 6 to 12 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or aryl having 6 to 12 carbon atoms, wherein Q is Si, M is Ti, and X 1 and X 2 are each independently hydrogen; halogen; alkyl having 1 to 12 carbon atoms; or alkenyl having 2 to 12 carbon atoms, a method for producing an olefin-based copolymer.
[Claim 10]
The method of claim 8, wherein the transition metal compound is one selected from the group consisting of compounds represented by the following Chemical Formulas 1-1 to 1-10. [Formula 1-1] [Formula 1-2] [Formula 1-3] [Formula 1-4] [Formula 1-5] [Formula 1-6] [Formula 1-7] [Formula 1-8] [Formula 1-8] 1-9] [Formula 1-10]
[Claim 11]
The method of claim 8, wherein the polymerization is carried out at 110°C to 160°C.