Cross-Citation with Related Applications
[2]
This application claims the benefit of priority based on Korean Patent Application 2018-0052043 filed on May 4, 2018, and all contents disclosed in the documents of the Korean patent applications are incorporated as a part of this specification.
[3]
[4]
technical field
[5]
The present invention relates to an ethylene/alpha-olefin copolymer exhibiting excellent physical properties by uniformly presenting a comonomer in the copolymer, and a method for preparing the same.
background
[6]
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.
[7]
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.
[8]
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.
[9]
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 implementing 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.
[10]
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 has excellent tear strength and drop impact strength. are doing
[11]
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.
[12]
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.
[13]
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
[14]
Accordingly, the present invention is to solve the problems of the prior art, and the molecular weight distribution is narrow, the comonomer is uniformly present to exhibit excellent physical properties, and in particular, an ethylene/alpha-olefin copolymer having excellent processability and a method for preparing the same would like to provide
[15]
Another object of the present invention is to provide a hot melt adhesive composition including the ethylene/alpha olefin copolymer and exhibiting excellent processability and adhesive properties.
means of solving the problem
[16]
In order to solve the above problems, according to an embodiment of the present invention, there is provided an ethylene/alpha-olefin copolymer satisfying the conditions of i) to iv) below:
[17]
i) a density of 0.85 to 0.89 g/cc,
[18]
ii) molecular weight distribution (MWD): 1.5 to 3.0,
[19]
iii) Viscosity: 6,000 cP to 40,000 cP when measured at a temperature of 180° C.,
[20]
iv) ReХRc ≤ 1.0
[21]
At this time, Re=kee/kec, Rc=kcc/kce,
[22]
kee represents the growth kinetics constant when ethylene is added to a growth chain having a terminal active point of an ethylene monomer, and kec represents the growth kinetics when an alpha olefin comonomer is added to a growth chain having a terminal active point of an ethylene monomer, kcc represents the growth reaction rate when an alpha olefin comonomer is added to the growth chain in which the terminal active point is an alpha olefin comonomer, and kce is the growth reaction when an ethylene monomer is added to the growth chain in which the terminal active point is an alpha olefin comonomer. Represents the rate constant.
Effects of the Invention
[23]
The ethylene/alpha-olefin copolymer according to the present invention has a low density and ultra-low molecular weight, and exhibits excellent impact strength and mechanical properties because the molecular weight distribution is narrow. In addition, the ethylene/alpha-olefin copolymer according to the present invention has excellent structural stability because the comonomer is uniformly distributed, and thus exhibits low complex viscosity in various temperature ranges and shear rates, and thus excellent It can show machinability.
[24]
Accordingly, when the ethylene/alpha-olefin copolymer according to the present invention is applied to a hot melt adhesive composition, the flowability or reactivity of the copolymer is relatively constant under various process conditions, so that the reaction efficiency can be improved, and excellent processability and adhesive properties A hot melt adhesive composition may be prepared.
Brief description of the drawing
[25]
1 shows the results of measuring the viscosity change according to the temperature change for Example 2 and Comparative Example 7 as an embodiment of the present invention.
[26]
2 shows the results of measuring the viscosity change according to the temperature change for Example 3 and Comparative Example 6 as an embodiment of the present invention.
[27]
3 shows the results of measuring the viscosity change according to the angular frequency change for Example 2 and Comparative Example 7 as an embodiment of the present invention.
[28]
4 shows the results of measuring the viscosity change according to the angular frequency change for Example 3 and Comparative Example 6 as an embodiment of the present invention.
Best mode for carrying out the invention
[29]
The terminology used herein is used to describe exemplary embodiments only, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as "comprise", "comprising" or "having" are intended to designate the presence of an embodied feature, step, element, or a combination thereof, but one or more other features or steps; It should be understood that the possibility of the presence or addition of components, or combinations thereof, is not precluded in advance.
[30]
Since the present invention may have various modifications and various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.
[31]
[32]
1. Ethylene/alpha-olefin copolymer
[33]
Hereinafter, the ethylene/alpha-olefin copolymer of the present invention will be described in detail.
[34]
The ethylene/alpha-olefin copolymer according to an embodiment of the present invention satisfies the following conditions i) to iv):
[35]
i) a density of 0.85 to 0.89 g/cc,
[36]
ii) molecular weight distribution (MWD): 1.5 to 3.0,
[37]
iii) Viscosity: 4,000 cP to 50,000 cP when measured at a temperature of 180° C.,
[38]
iv) ReХRc ≤ 1.0
[39]
At this time, Re=kee/kec, Rc=kcc/kce,
[40]
kee represents the growth kinetics constant when ethylene is added to a growth chain having a terminal active point of an ethylene monomer, and kec represents the growth kinetics when an alpha olefin comonomer is added to a growth chain having a terminal active point of an ethylene monomer, kcc represents the growth reaction rate when an alpha olefin comonomer is added to the growth chain in which the terminal active point is an alpha olefin comonomer, and kce is the growth reaction when an ethylene monomer is added to the growth chain in which the terminal active point is an alpha olefin comonomer. Represents the rate constant.
[41]
Crosslinking between the copolymers is caused by vinyl and vinylidene containing a double bond. The ethylene/alpha-olefin copolymer according to the embodiment is polymerized by adding an optimized amount of hydrogen together with a catalyst to be described later during polymerization, The incorporation of the alpha-olefin comonomer becomes uniform, so that the ReХRc value meets the above range, which can be said to indicate that the comonomer is uniformly distributed in the polymer. In general, the shear fluidization properties can be measured by measuring the complex viscosity as a function of frequency, but these copolymers can have very good processability because the complex viscosity remains low over a specific temperature and angular frequency range. have.
[42]
[43]
Accordingly, the present invention uses the catalyst as described below and adds an optimal amount of hydrogen during polymerization to simultaneously satisfy the conditions of i) to iv), thereby providing physical properties, particularly long-term properties, of the ethylene/alpha olefin copolymer. can be greatly improved.
[44]
Specifically, the ethylene/alpha-olefin copolymer according to an embodiment of the present invention has a density of 0.85 g/cc to 0.89 additionally measured according to ASTM D-792 under conditions satisfying the physical property requirements as described above. g/cc. Specifically, the density may be 0.855 g/cc or more, or 0.86 g/cc or more, or 0.865 g/cc or more, and 0.89 g/cc or less, or 0.885 g/cc or less, or 0.880 g/cc or less.
[45]
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, etc. In the case of a copolymer, the effect is large by the content of the comonomer. An olefin copolymer can be prepared, and the amount in which the comonomer can be introduced into the copolymer may depend on the copolymerizability of the catalyst, that is, the properties of the catalyst.
[46]
In the present invention, it is possible to introduce a large amount of comonomer by using a catalyst composition including a transition metal compound having a specific structure. As a result, the ethylene/alpha-olefin copolymer according to an exemplary embodiment of the present invention may have a low density as described above, and, as a result, may exhibit excellent processability. More specifically, the ethylene/alpha-olefin copolymer may have a density of preferably 0.860 g/cc to 0.885 g/cc, more preferably 0.865 g/cc to 0.880 g/cc, and in this case, according to the density control The effect of maintaining mechanical properties and improving impact strength is more remarkable.
[47]
[48]
In addition, the ethylene/alpha-olefin copolymer according to an embodiment of the present invention has a viscosity of 50,000 cP or less, measured at 180° C., under the conditions satisfying the low density characteristics as described above. More specifically, the viscosity of the ethylene/alpha-olefin copolymer may be 40,000 cP or less, 37,000 cP or less, or 35,000 cP or less, 4,000 cP or more, or 6,000 cP or more, or 7,000 cP or more, or 8,500 cP or more.
[49]
In addition, the ethylene/alpha-olefin copolymer according to an embodiment of the present invention has a molecular weight distribution (MWD) of 1.5 to 3.0. Specifically, the molecular weight distribution may be 2.5 or less, and more specifically, 1.7 or more, or 1.8 or more, or 1.9 or more, and 2.3 or less, or 2.1 or less, or 2.0 or less.
[50]
In general, when two or more kinds of monomers are polymerized, molecular weight distribution (MWD) increases, and as a result, impact strength and mechanical properties decrease, and blocking phenomenon occurs. In contrast, in the present invention, by adding an optimal amount of hydrogen during the polymerization reaction, the molecular weight and molecular weight distribution of the prepared ethylene/alpha-olefin copolymer is reduced, and as a result, the impact strength and mechanical properties are improved.
[51]
Meanwhile, in the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC), and the molecular weight distribution is from the ratio of Mw / Mn. can be calculated.
[52]
In addition, the ethylene/alpha-olefin copolymer according to an embodiment of the present invention has ReХRc ≤ 1.0. In this case, Re=kee/kec, Rc=kcc/kce, and kee, kec, kcc and kce represent the growth reaction rate constants as previously defined.
[53]
The growth rate constants such as kee, kec, kcc and kce can be obtained by measuring the arrangement of monomers using C13 NMR, and Re and Rc can be calculated through this. When the calculated value of the product of Re and Rc (ReХRc) is 1.0 or less, more specifically, 0.95 or less, the ethylene/alpha-olefin copolymer is highly likely to be formed into an alternating copolymer, and the product of Re and Rc When the value (ReХRc) exceeds 1.0, it is highly likely that the ethylene-alpha olefin copolymer is formed into a block copolymer. The term "alternating copolymer" refers to a form (eg, -ABABABAB-) in which two monomer components (eg, A, B) constituting the copolymer are alternately polymerized (eg, -ABABABAB-), and the term "block copolymer" is a public In a coalescence, one monomer component (A) is successively polymerized to form a block, and then another monomer component (B) is subsequently polymerized to form a block (eg -AAAABBBB-).
[54]
Therefore, the ethylene-alpha olefin copolymer according to an embodiment of the present invention has a value of the product of Re and Rc (ReХRc) of 1.0 or less, more specifically, 0.95 or less, so that the alpha-olefin comonomer is continuously polymerized and , may be an alternating copolymer evenly distributed in the polymer backbone. As such, since the alpha-olefin comonomer is evenly distributed in the polymer main chain, it exhibits excellent structural stability, and also improves reaction efficiency through a uniform reaction when preparing a hot melt adhesive composition using the ethylene-alpha olefin copolymer. and, as a result, it is possible to improve workability together with adhesiveness.
[55]
Specifically, like the ethylene/alpha-olefin copolymer according to an embodiment of the present invention, when the above conditions are satisfied, there is little change in complex viscosity within a specific range of temperature and shear rate during processing. It can exhibit very good processability.
[56]
The ethylene/alpha-olefin copolymer according to an embodiment of the present invention is a copolymer that is prepared according to a specific manufacturing method, and satisfies the density, molecular weight distribution, viscosity, and ReХRc value as described above within a specific range, and has a low density. At the same time, it may be an ethylene/alpha-olefin copolymer having an ultra-low molecular weight and uniform distribution of comonomers in the copolymer, and the hot melt adhesive composition prepared through this may have excellent physical properties such as impact strength and adhesion.
[57]
[58]
The ethylene/alpha-olefin copolymer according to an embodiment of the present invention may be a polymer having an ultra-low molecular weight having a weight average molecular weight (Mw) of 15,000 to 45,000 g/mol. More specifically, the weight average molecular weight may be 17,000 g/mol or more, or 19,000 g/mol or more, and 40,000 g/mol or less, or 37,000 g/mol or less, or 35,000 g/mol or less.
[59]
In addition, the ethylene/alpha-olefin copolymer according to an embodiment of the present invention may have a number average molecular weight (Mn) of 5,000 to 35,000. More specifically, the number average molecular weight may be 7,000 or more, or 8,000 or more, or 9,000 or more, and may be 30,000 or less, or 25,000 or less.
[60]
In addition, the ethylene/alpha-olefin copolymer may have a melt index (MI) of 200 to 1,300 dg/min, specifically, the melt index may be 400 dg/min or more, 500 dg/min or more, and 1,200 dg /min or less, it may be 1,000 dg/min or less. The melt index (MI) is a value measured by ASTM D-1238 (Condition E, 190°C, 2.16 kg load).
[61]
When the weight average molecular weight and melt index satisfy the above ranges, it may be suitable for application to a hot melt adhesive composition, and a significant improvement in processability can be expected in relation with viscosity. That is, the viscosity affecting the mechanical properties, impact strength, and processability of the ethylene/alpha-olefin copolymer can be controlled by adjusting the amount of catalyst along with the type of catalyst used in the polymerization process. By satisfying the viscosity range, improved processability can be exhibited while maintaining excellent mechanical properties.
[62]
[63]
In addition, in the ethylene/alpha-olefin copolymer according to an embodiment of the present invention, the number of unsaturated functional groups per 1000 carbon atoms in the copolymer may be 0.8 or less. More specifically, the number of unsaturated functional groups is 0.6 or less, or 0.5 or less, or 0.45 or less, or 0.42 or less, or 0.41 or less, 0.1 or more, or 0.20 or less per 1000 carbon atoms constituting the copolymer. or more or 0.3 or more. The number of unsaturated functional groups in the copolymer is possible through control of the polymerization temperature and the amount of hydrogen input during manufacture. The ethylene/alpha-olefin copolymer according to the present invention has a low number of unsaturated functional groups as described above, so that it is stored for a long time at high temperature (heat aging) It can exhibit excellent long-term physical properties with small changes in color change, molecular weight and viscosity with time.
[64]
In the present invention, the number of unsaturated functional groups in the copolymer may be calculated from the results of NMR analysis. Specifically, after dissolving the copolymer in chloroform-d (w/TMS) solution, using an Agilent 500 MHz NMR equipment, the acquisition time of 2 seconds at room temperature, 16 measurements at a pulse angle of 45°, and the TMS peak in 1H NMR were measured. Corrected to 0 ppm, checked the CH 3 related peak (triplet) of 1-octene at 0.88 ppm , and CH 2 related peak (broad singlet) of ethylene at 1.26 ppm, respectively, and corrected the CH 3 peak integral value to 3. to calculate the content, and also, the number of double bonds can be calculated based on the integral value of the double bonds in the 4.5 to 6.0 ppm region.
[65]
[66]
In addition, the ethylene/alpha-olefin copolymer according to an embodiment of the present invention may have a crystallization temperature (Tc) of 45° C. or higher. More specifically, the crystallization temperature may be 50 °C or higher, or 51 °C or higher, 60 °C or lower, or 58 °C or lower, or 56 °C or lower. This high crystallization temperature is due to the uniform distribution of the comonomer in the ethylene/alpha-olefin copolymer, and by having the above temperature range, excellent structural stability may be exhibited.
[67]
In addition, the ethylene/alpha-olefin copolymer according to an embodiment of the present invention may have a melting temperature (Tm) of 60 to 80°C. More specifically, the melting temperature may be 65 °C or higher, or 69 °C or higher, or 70 °C or higher, and 75 °C or lower, or 74.5 °C or lower, or 74 °C or lower. By having a melting temperature in such a temperature range, excellent thermal stability can be exhibited.
[68]
In the present invention, the crystallization temperature and melting temperature of the ethylene/alpha-olefin copolymer may be measured using a Differential Scanning Calorimeter (DSC). Specifically, the copolymer is heated to 150° C. and maintained for 5 minutes, then lowered to 20° C., and then the temperature is increased again. At this time, the rate of rise and fall of the temperature are controlled at 10 °C/min, respectively, and the result measured in the section where the second temperature rises is the melting temperature, and the result measured in the section where the temperature is decreased is the crystallization temperature.
[69]
[70]
In addition, in the ethylene/alpha-olefin copolymer according to an embodiment of the present invention, the alpha-olefinic monomer as a comonomer may be an olefinic monomer having 4 to 20 carbon atoms. Specific examples include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetra decene, 1-hexadecene, or 1-eicosene, and the like, and any one of them or a mixture of two or more thereof may be used.
[71]
Among them, considering that the improvement effect is remarkable when applied to the hot melt adhesive composition, the alpha-olefin monomer may be 1-butene, 1-hexene, or 1-octene, and most preferably 1-octene.
[72]
In addition, in the ethylene/alpha-olefin copolymer, the content of alpha-olefin, which is the comonomer, may be appropriately selected within the range satisfying the above-mentioned physical property requirements, specifically more than 0 and 99 mol% or less, or It may be 10 to 50 mol%.
[73]
[74]
The ethylene/alpha-olefin copolymer according to another embodiment of the present invention satisfies the following conditions i) to vii).
[75]
i) a density of 0.85 to 0.89 g/cc,
[76]
ii) molecular weight distribution (MWD): 1.5 to 3.0,
[77]
iii) Viscosity: 4,000 cP to 50,000 cP as measured at a temperature of 180° C.,
[78]
iv) the total number of unsaturated functional groups per 1000 carbon atoms: 0.8 or less;
[79]
v) number average molecular weight (Mn): 9,000 to 25,000,
[80]
vi) Melt index (MI) at 190°C and 2.16 kg load according to ASTM D1238: 200 to 1,300 dg/min, and
[81]
vii) ReХRc ≤ 1.0
[82]
At this time, Re=kee/kec, Rc=kcc/kce,
[83]
kee represents the growth kinetics constant when ethylene is added to a growth chain having a terminal active point of an ethylene monomer, and kec represents the growth kinetics when an alpha olefin comonomer is added to a growth chain having a terminal active point of an ethylene monomer, kcc represents the growth reaction rate when an alpha olefin comonomer is added to the growth chain in which the terminal active point is an alpha olefin comonomer, and kce is the growth reaction when an ethylene monomer is added to the growth chain in which the terminal active point is an alpha olefin comonomer. Represents the rate constant.
[84]
The copolymer as described above may realize the same effects as described above, and since the number of total unsaturated functional groups is small, improvement in effects such as long-term stability can be expected.
[85]
[86]
2. Method for preparing ethylene/alpha-olefin copolymer
[87]
On the other hand, the ethylene/alpha-olefin copolymer having the above physical properties is ethylene and alpha-olefin by adding hydrogen at 45 to 100 cc/min in the presence of a catalyst composition including a transition metal compound of Formula 1 below. It can be prepared by a manufacturing method comprising the step of polymerizing the monomer. Accordingly, according to another embodiment of the present invention, there is provided a method for preparing the above-described ethylene/alpha-olefin copolymer:
[88]
[Formula 1]
[89]

[90]
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,
[91]
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,
[92]
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; or aryl amido having 6 to 20 carbon atoms; Phenyl substituted with one or more selected from the group consisting of 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 ego,
[93]
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,
[94]
Q is Si or C;
[95]
M is a Group 4 transition metal,
[96]
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; or arylamino having 6 to 20 carbon atoms.
[97]
[98]
As described above, when the transition metal compound having the structure of Formula 1 is included in the catalyst composition to polymerize ethylene and alpha-olefin-based comonomers with hydrogen, as described above, low-density and ultra-low molecular weight ethylene/alpha-olefin copolymers In this ethylene/alpha-olefin copolymer, the number of unsaturated functional groups is extremely small, and the alpha-olefin comonomer is uniformly incorporated in the copolymer, so that the branched chain bonded to the main chain of the copolymer is constant, so it is relatively low. Due to the low crystallinity and high crystallinity content, it is possible to prepare a copolymer having a uniform crystallinity distribution, and thus processability may be excellent even at a low processing temperature.
[99]
[100]
The substituents in Formula 1 will be described in more detail as follows.
[101]
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.
[102]
Specifically, 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.
[103]
More specifically, R 1 may be hydrogen or alkyl having 1 to 12 carbon atoms.
[104]
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.
[105]
Specifically, 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.
[106]
More specifically, R 2a to R 2e are each independently hydrogen; alkyl having 1 to 12 carbon atoms; Or it may be alkoxy having 1 to 12 carbon atoms.
[107]
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 a phenyl substituted with one or more selected from the group consisting of halogen, alkyl having 1 to 12 carbons, cycloalkyl having 3 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 12 carbons, and phenyl.
[108]
Specifically, 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,
[109]
More specifically, R 3 is hydrogen; alkyl having 1 to 12 carbon atoms; or phenyl.
[110]
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.
[111]
Specifically, 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.
[112]
More specifically, R 4 and R 5 are each independently hydrogen; Or it may be an alkyl having 1 to 12 carbon atoms,
[113]
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.
[114]
Specifically, 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; 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.
[115]
More specifically, R 6 to R 9 may each independently be hydrogen or methyl.
[116]
In addition, Q may be Si, and M may be Ti.
[117]
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; Or it may be an arylamino having 6 to 12 carbon atoms.
[118]
Specifically, 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.
[119]
More specifically, X 1 and X 2 may each independently be hydrogen or alkyl having 1 to 12 carbon atoms.
[120]
[121]
In the transition metal compound of Formula 1, cyclopentadiene to which benzothiophene is fused by a cyclic bond, and an amido group (NR 1 ) are stably cross-linked by Q (Si, C, N or P), Group 4 transition metals form a coordinated structure. When applied to olefin polymerization using the catalyst composition, it is possible to produce polyolefins having characteristics such as high activity, high molecular weight, and high copolymerizability even at a high polymerization temperature.
[122]
Furthermore, the transition metal compound of Formula 1 has a structure in which an amido group (N-R1) is crosslinked by Q (Si, C, N, P) and a substituted or unsubstituted phenyl group is bonded to Q. , can be cross-linked more stably, and have excellent electronic stability when coordinated with a transition metal.
[123]
In the case of a transition metal compound having such a structure, since copolymerizability is excellent due to the phenyl group, a low-density copolymer can be prepared even with a small amount of comonomer compared to a catalyst that does not have the same core structure as the transition metal compound of Formula 1 At the same time, it is possible to describe the advantage that high-temperature polymerization is possible because of the excellent molecular weight level and that hydrogen can be stably added.
[124]
That is, in the present invention, an ethylene/alpha-olefin copolymer having a narrow molecular weight distribution and a uniform comonomer distribution along with an ultra-low molecular weight is provided by using the transition metal compound as described above, but by adding hydrogen in an optimized content during the polymerization reaction. Due to the electronic / structural stability of the transition metal compound, the incorporation of hydrogen is advantageous, and the termination reaction is uniformly generated by hydrogen in the polymerization reaction to prepare an ultra-low molecular weight copolymer having a narrow molecular weight distribution. possible effects can be expected.
[125]
[126]
More specifically, specific examples of the compound of Formula 1 may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.
[127]
[Formula 1-1] [Formula 1-2] [Formula 1-3]
[128]

[129]
[Formula 1-4] [Formula 1-5] [Formula 1-6]
[130]

[131]
[Formula 1-7] [Formula 1-8]
[132]

[133]
[Formula 1-9] [Formula 1-10]
[134]

[135]
[136]
Meanwhile, in the preparation of the ethylene/alpha-olefin copolymer according to an embodiment of the present invention, the catalyst composition may further include a cocatalyst to activate the transition metal compound of Formula 1 above.
[137]
The promoter is an organometallic compound including a Group 13 metal, and specifically, may include at least one of a compound of Formula 2 below, a compound of Formula 3 below, and a compound of Formula 4 below.
[138]
[Formula 2]
[139]
R 41 -[Al(R 42 )-O] n -R 43
[140]
In Formula 2,
[141]
R 41 , R 42 and R 43 are each independently any one of hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen;
[142]
n is an integer greater than or equal to 2,
[143]
[Formula 3]
[144]
D(R 44 ) 3
[145]
In Formula 3, D is aluminum or boron,
[146]
R 44 is each independently any one of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
[147]
[Formula 4]
[148]
[LH] + [Z(A) 4 ] - or [L] + [Z(A) 4 ] -
[149]
In Formula 4,
[150]
L is a neutral or cationic Lewis base, H is a hydrogen atom,
[151]
Z is a group 13 element, A is each independently a hydrocarbyl group having 1 to 20 carbon atoms; a hydrocarbyloxy group having 1 to 20 carbon atoms; and one or more of the substituents in which one or more hydrogen atoms of these substituents are substituted with one or more substituents among halogen, a C1-C20 hydrocarbyloxy group, and a C1-C20 hydrocarbylsilyl group.
[152]
[153]
More specifically, the compound of Formula 2 may be an alkylaluminoxane-based compound to which repeating units are bonded in a linear, circular or network form, and specific examples include methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, or tert-butylaluminoxane etc. are mentioned.
[154]
In addition, specific examples of the compound of Formula 3 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclo Pentyl aluminum, 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 or tributyl boron, and in particular, may be selected from trimethyl aluminum, triethyl aluminum or triisobutyl aluminum.
[155]
In addition, the compound of Formula 4 may include a borate-based compound in the form of a trisubstituted ammonium salt, a dialkyl ammonium salt, or a trisubstituted phosphonium salt. More specific examples include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, methyltetradecyclo Octadecylammonium tetraphenylborate, N,N-dimethylaninium tetraphenylborate, N,N-diethylaninium tetraphenylborate, N,N-dimethyl(2,4,6-trimethylanilium)tetraphenylborate, Trimethylammonium tetrakis(pentafluorophenyl)borate, methylditetradecylammonium tetrakis(pentaphenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium, tetrakis(pentafluoro Phenyl) borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl) ) borate, N,N-dimethylanilium tetrakis(pentafluorophenyl)borate, N,N-diethylaniniumtetrakis(pentafluorophenyl)borate, N,N-dimethyl (2,4,6- Trimethylaninium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis(2,3,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis(2,3,4,6-tetrafluoro Rophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-, tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N,N-dimethylaninium tetrakis (2,3,4, 6-tetrafluorophenyl)borate, N,N-diethylaninium tetrakis(2,3,4,6-tetrafluorophenyl)borate or N,N-dimethyl-(2,4,6-trimethylanyl) borate compounds in the form of trisubstituted ammonium salts such as nium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate; Borates in the form of dialkylammonium salts such as dioctadecylammonium tetrakis(pentafluorophenyl)borate, ditetradecylammonium tetrakis(pentafluorophenyl)borate, or dicyclohexylammonium tetrakis(pentafluorophenyl)borate compound; or triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate or tri(2,6-, dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl ) borate compounds in the form of trisubstituted phosphonium salts such as borate.
[156]
By using such a cocatalyst, the molecular weight distribution of the finally prepared ethylene/alpha-olefin copolymer becomes more uniform, and polymerization activity can be improved.
[157]
The cocatalyst may be used in an appropriate amount so that the activation of the transition metal compound of Formula 1 may be sufficiently progressed.
[158]
[159]
In addition, the catalyst composition may include the transition metal compound of Formula 1 in a supported form on a carrier.
[160]
When the transition metal compound of Formula 1 is supported on the carrier, the weight ratio of the transition metal compound to the carrier may be 1:10 to 1:1,000, more specifically 1:10 to 1:500. When the carrier and the transition metal compound are included in a mid-ratio ratio within the above range, an optimal shape may be exhibited. In addition, when the cocatalyst is supported on the carrier together, the weight ratio of the cocatalyst to the carrier may be 1:1 to 1:100, more specifically 1:1 to 1:50. When the cocatalyst and the carrier are included in the above weight ratio, it is possible to improve the catalytic activity and optimize the microstructure of the polymer to be prepared.
[161]
On the other hand, as the carrier, silica, alumina, magnesia, or a mixture thereof may be used, or by drying these materials at a high temperature to remove moisture from the surface, a hydroxyl group or a siloxane group having high reactivity on the surface. may be used. In addition, the high-temperature dried carriers may further include an oxide, carbonate, sulfate, or nitrate component such as Na 2 O, K 2 CO 3 , BaSO 4 and Mg(NO 3 ) 2 .
[162]
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, and the reaction site with the promoter decreases.
[163]
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.
[164]
[165]
Meanwhile, the polymerization reaction of the ethylene/alpha-olefin copolymer may be performed by continuously adding hydrogen in the presence of the catalyst composition and continuously polymerizing ethylene and an alpha-olefin-based monomer.
[166]
In this case, the hydrogen gas serves to suppress the rapid reaction of the transition metal compound in the initial stage of polymerization and terminate the polymerization reaction. Accordingly, an ethylene/alpha-olefin copolymer having an ultra-low molecular weight and narrow molecular weight distribution can be effectively prepared by controlling the use and usage of the hydrogen gas.
[167]
The hydrogen gas may be introduced at a rate of 45 to 100 cc/min, more specifically, 50 to 95 cc/min. When added under the above conditions, the ethylene/alpha-olefin polymer to be prepared may implement the physical properties in the present invention. If the content of hydrogen gas is added to less than 45 cc/min, the polymerization reaction is not uniformly terminated, making it difficult to prepare an ethylene/alpha-olefin copolymer having desired physical properties, and exceeding 100 cc/min In this case, there is a risk that the termination reaction occurs too quickly to produce an ethylene/alpha-olefin copolymer having an excessively low molecular weight. When the above range is satisfied, the reactivity ratio between monomers can be easily controlled, and accordingly A copolymer in which the olefinic comonomer is uniformly incorporated can be prepared.
[168]
[169]
In addition, the polymerization reaction may be performed at 80 to 200° C., but by controlling the polymerization temperature together with the hydrogen input amount, the number of unsaturated functional groups and the monomer reactivity ratio in the ethylene/alpha-olefin copolymer can be more easily controlled. Accordingly, specifically, the polymerization reaction may be 100 to 150 ℃, more specifically 100 to 140 ℃.
[170]
[171]
In addition, during the polymerization reaction, an organoaluminum compound for removing moisture in the reactor is further added, and the polymerization reaction may proceed in the presence thereof. Specific examples of the organoaluminum compound include trialkylaluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride or alkyl aluminum sesqui halide, and more specific examples thereof include Al (C 2 H 5 ) 3 , Al(C 2 H 5 ) 2 H, Al(C 3 H 7 ) 3 , Al(C 3 H 7 ) 2 H, Al(iC 4 H 9 ) 2 H, Al(C 8 H 17 ) ) 3 , Al(C 12 H 25 ) 3 , Al(C 2 H 5 )(C 12 H 25 ) 2 , Al(iC 4 H 9 )(C 12 H 25 ) 2 , Al(iC 4 H 9 ) 2 H , Al(iC 4 H 9 ) 3 , (C 2 H 5 ) 2 AlCl, (iC 3 )H 9 ) 2 AlCl or (C 2 H 5 ) 3 A 12 Cl 3 , and the like. Such an organoaluminum compound may be continuously added to the reactor, and may be added in a ratio of about 0.1 to 10 moles per 1 kg of the reaction medium fed into the reactor for proper moisture removal.
[172]
Also, the polymerization pressure may be from about 1 to about 100 Kgf/cm 2 , preferably from about 1 to about 50 Kgf/cm 2 , more preferably from about 5 to about 30 Kgf/cm 2 .
[173]
In addition, when a transition metal compound is used in a supported form on a carrier, the transition metal compound is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof and toluene, benzene. It may be dissolved or diluted in an aromatic hydrocarbon solvent, such as dichloromethane, or a hydrocarbon solvent substituted with a chlorine atom, such as chlorobenzene. The solvent used here is preferably used by treating a small amount of alkyl aluminum to remove a small amount of water or air acting as a catalyst poison, and it is also possible to further use a cocatalyst.
[174]
The ethylene/alpha-olefin copolymer prepared by the above-described preparation method has a narrow molecular weight distribution with low density and ultra-low molecular weight, and at the same time minimizes the number of unsaturated functional groups in the polymer, and satisfies the condition of ReХRc ≤ 1.0. Accordingly, excellent physical properties, particularly excellent long-term properties, can be exhibited, and when applied to a hot melt adhesive composition, processability can be improved along with adhesive properties.
[175]
[176]
Accordingly, according to another embodiment of the present invention, there is provided a hot melt adhesive composition comprising the above-described ethylene/alpha-olefin copolymer.
[177]
The hot melt adhesive composition may be prepared and used according to a conventional method, except that the ethylene/alpha-olefin copolymer is included as a main component.
Modes for carrying out the invention
[178]
Example
[179]
Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and thus the content of the present invention is not limited thereto.
[180]
[181]
[Synthesis Example: Preparation of transition metal compound]
[182]
Step 1: Preparation of Ligand Compound (1a-1)
[183]
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.
[184]
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.
[185]
(1a-1)
[186]

[187]
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)
[188]
[189]
Step 2: Preparation of transition metal compound (1a)
[190]
In a 100 mL Schlenk flask, add 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 this order and stirred at room temperature overnight. . After stirring, the mixture was dried in vacuo, 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.
[191]
(1a)
[192]

[193]
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)
[194]
[195]
[Preparation of ethylene/alpha-olefin copolymer]
[196]
Example 1
[197]
After filling a 1.5L autoclave continuous process reactor with hexane solvent (5.0 kg/h) and 1-octene (1.00 kg/h), the temperature at the top of the reactor was preheated to 150°C. Triisobutylaluminum compound (0.05 mmol/min), transition metal compound (1a) (0.40 μmol/min) prepared in the above synthesis example as a catalyst, dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (1.20 μmol) /min) was simultaneously introduced into the reactor. Then, ethylene (0.87 kg/h) and hydrogen gas (50 cc/min) were introduced into the autoclave reactor, maintained at a pressure of 89 bar and a polymerization temperature of 125° C. for at least 60 minutes, and the copolymerization reaction was continuously performed to obtain a copolymer. prepared.
[198]
Next, the remaining ethylene gas was drained, and the obtained copolymer-containing solution was dried in a vacuum oven for at least 12 hours, and then physical properties of the obtained copolymer were measured.
[199]
[200]
Examples 2 to 7, and Comparative Examples 1 to 7
[201]
A polymer was prepared in the same manner as in Example 1, except that the reactants were added in the amounts shown in Table 1 below.
[202]
[Table 1]
Catalyst dosage (μmol/min) Cocatalyst dosage (μmol/min) 1-C8 dosage (kg/h) TiBAl (mmol/min) Polymerization temperature (℃) H 2 Dosage (cc/min)
Example 1 0.40 1.20 1.00 0.05 125 50
Example 2 0.40 1.20 1.00 0.05 125 75
Example 3 0.40 1.20 1.00 0.05 125 80
Example 4 0.40 1.20 1.00 0.05 125 95
Example 5 0.20 0.60 1.10 0.05 125 85
Example 6 0.35 1.05 1.15 0.05 145 50
Example 7 0.35 1.05 1.15 0.05 145 55
Comparative Example 1 0.70 2.10 2.00 0.05 150 0
Comparative Example 2 0.40 1.20 1.00 0.05 125 0
Comparative Example 3 0.40 1.20 1.00 0.05 125 10
Comparative Example 4 0.40 1.20 1.00 0.05 125 15
Comparative Example 5 0.40 1.20 1.00 0.05 125 130
Comparative Example 6 0.26 0.78 1.20 0.05 125 35
Comparative Example 7 0.65 1.95 2.20 0.05 160 0
[203]
* In Comparative Examples 6 and 7, [Me 2 Si(Me 4 C 5 )NtBu]Ti(CH 3 ) 2 was used as a catalyst.
[204]
[205]
[Evaluation of physical properties of olefin polymers]
[206]
Experimental Example 1
[207]
The physical properties of the ethylene/alpha-olefin copolymers prepared in Examples and Comparative Examples were measured in the following manner and are shown in Table 2.
[208]
1) Density (Density, g/cm 3 ): Measured according to ASTM D-792.
[209]
2) Viscosity (cP) : It was measured according to the following method using a Brookfield RVDV3T viscometer. Specifically, the sample is placed in a 13ml sample chamber, heated to 180°C using a Brookfield Thermosel, and when the sample is completely melted, lower the viscometer device to fix the spindle in the sample chamber, and the spindle (SC-29 hot-melt spindle) ) was read for at least 20 minutes or until the value was stabilized after fixing the rotation speed to 20 rpm, and the final value was recorded. For reference, the measurement limit of viscosity is 50,000 cP.
[210]
3) Melting temperature (Tm, ℃) : The melting temperature of the polymer was measured using a Differential Scanning Calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 150° C. and maintained for 5 minutes, then lowered to -100° C. and then the temperature was increased again. At this time, the rate of rise and fall of the temperature was adjusted to 10 °C/min, respectively. The melting temperature was taken as the maximum point of the endothermic peak measured in the section where the second temperature was increased.
[211]
4) Crystallization temperature (Tc, ℃) : It was carried out in the same manner as when the melting temperature was measured using DSC, and the maximum point of the exothermic peak was defined as the crystallization temperature from the curve appearing while decreasing the temperature.
[212]
5) Weight average molecular weight (g/mol) and molecular weight distribution (MWD) : The number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC: gel permeation chromatography, PL GPC220) under the following conditions. Each was measured, and molecular weight distribution was calculated by dividing the weight average molecular weight by the number average molecular weight.
[213]
- Column: PL Olexis
[214]
- Solvent: TCB (Trichlorobenzene)
[215]
- Flow rate: 1.0 ml/min
[216]
- Sample concentration: 1.0 mg/ml
[217]
- Injection volume: 200 μl
[218]
- Column temperature: 160℃
[219]
- Detector: Agilent High Temperature RI detector
[220]
- Standard: Polystyrene (corrected by cubic function)
[221]
6) Measurement of monomer reactivity ratio (Re, Rc) : Dissolve the ethylene-alpha olefin copolymer prepared in Examples and Comparative Examples in a solvent (1,1,2,2-tetrachloroethane-d2 (TCE-d2)) Then, about 0.4ml was put into a tube having a diameter of 5mm and a length of 18cm, and then the tube was placed in a 13C NMR spectrometer, and the spectrometer frequency 150MHz, temperature 100℃, d1 (relaxation delay time) 3s, and Scans 4k conditions kee, kec, kcc and kce values ​​were measured, and the monomer reactivity ratio was calculated by substituting them into Equations 3 and 4. The measurement of the monomer reactivity ratio is limited in the present invention together with Examples 1 to 7 Only Comparative Examples 6 and 7 satisfying the viscosity were performed.
[222]
[Equation 3]
[223]
Re(reactivity ratio of ethylene monomer)=kee/kec
[224]
[Equation 4]
[225]
Rc (reactivity ratio of alpha olefin comonomer)=kcc/kce
[226]
(In Equations 3 and 4, kee represents the growth kinetics constant when ethylene is added to the growth chain having the terminal active point of the ethylene monomer, and kec is the addition of the alpha olefin comonomer to the growth chain having the terminal active point of the ethylene monomer. represents the growth kinetics when an alpha olefin comonomer is added to the growth chain where the terminal active point is an alpha olefin comonomer, and kce is the growth kinetics when the terminal active point is an alpha olefin comonomer. It represents the growth kinetics constant when ethylene monomer is added.)
[227]
[Table 2]
Density (g/cc) Tc / Tm( o C) Viscosity (cP) Mw (g/mol) Molecular Weight Distribution (MWD) Monomer Reactivity Ratio
Re Rc Re×Rc
Example 1 0.873 50.6 / 66.5 35000 34900 1.98 7.31 0.13 0.95
Example 2 0.875 52.0 / 68.1 17000 24400 1.96 9.30 0.10 0.93
Example 3 0.876 52.3 / 68.9 13500 22400 1.98 6.71 0.14 0.94
Example 4 0.877 53.2 / 69.7 8500 19500 1.77 8.09 0.11 0.89
Example 5 0.875 52.2 / 68.3 17000 24500 1.96 8.53 0.11 0.94
Example 6 0.876 52.2 / 68.8 13500 22300 2.00 8.82 0.11 0.97
Example 7 0.876 52.5 / 69.1 8800 1970 1.99 7.83 0.12 0.94
Comparative Example 1 0.872 49.7 / 66.0 >50000 46800 2.14 - - -
Comparative Example 2 0.874 51.5 / 67.6 >50000 75400 2.08 - - -
Comparative Example 3 0.874 51.3 / 67.8 >50000 57700 2.09 - - -
Comparative Example 4 0.873 50.5 / 66.3 >50000 48700 2.08 - - -
Comparative Example 5 0.879 55.7 / 72.7 3500 14600 1.97 - - -
Comparative Example 6 0.876 56.1 / 73.2 13900 22800 1.94 1.29 1.56 1.50
Comparative Example 7 0.875 55.3 / 73.1 15800 26700 2.24 8.11 0.25 2.03
[228]
In Table 2, "-" means no measurement.
[229]
[230]
Referring to Table 2, the ethylene/alpha-olefin copolymers of Examples 1 to 7 prepared by using the catalyst composition containing the transition metal compound according to the present invention and adding hydrogen during the polymerization reaction, Comparative Examples 1 to 7 Compared with , it has a low density and an ultra-low molecular weight (evaluated by viscosity), a narrow molecular weight distribution, and a ReХRc value of 1.0 or less, more specifically 0.97 or less.
[231]
Specifically, in the case of Comparative Examples 1 to 4 in which hydrogen is not added or more than a certain amount is not added, a copolymer having a fairly high molecular weight was prepared, and it can be predicted that the physical properties are not good because the molecular weight distribution is wide. In addition, in Comparative Example 5, in which hydrogen was added excessively, polymerization was prematurely terminated by hydrogen, and it can be seen that a copolymer having a large molecular weight was prepared.
[232]
In addition, Comparative Example 7, in which a catalyst other than the catalyst according to the present invention was applied without adding hydrogen, showed a fairly wide molecular weight distribution, and the ReХRc value exceeded 1.0, resulting in a large numerical value of 2.03, resulting in a non-uniform air It can be predicted that a coalescence has been prepared. It can be confirmed through Comparative Example 6 that this non-uniformity does not disappear even when hydrogen is added.
[233]
In the case of the catalysts used in Comparative Examples 6 and 7, compared to the catalysts applied in Examples 1 to 7, a high molecular weight polymer could not be prepared and the copolymerizability for the comonomer was poor, so hydrogen could be added to control the polymerization reaction. It can be seen that the monomer reactivity ratio was not controlled due to the absolute small amount of the present, and the results show that the ReХRc value was larger than 1.0 because the comonomer was not uniformly incorporated even though the viscosity was low. After all, this phenomenon is a phenomenon that can be inferred that the catalysts of Comparative Examples 6 and 7 will reach a level where processing is impossible due to very low viscosity when more hydrogen is added.
[234]
[235]
Experimental Example 2
[236]
With respect to Example 2 and Comparative Example 7, the viscosity change was measured while the frequency was fixed at 6.28 rad/s (1 Hz) and the temperature was increased, and is shown in FIG. is measured and shown in FIG. 2, and the viscosity change is measured while changing the angular frequency at 80 ° C for Example 2 and Comparative Example 7 and shown in FIG. 3, and for Example 3 and Comparative Example 6 while changing the angular frequency at 80 ° C. The viscosity change was measured and shown in FIG. 4 . The measurement method of the viscosity is the same as described above.
[237]
In FIG. 1, Example 2 shows a lower complex viscosity in all temperature regions compared to Comparative Example 7 having a similar density, and Example 3 in FIG. It exhibits low complex viscosity in the temperature range. Therefore, the ethylene/alpha-olefin copolymer of the present invention is advantageous in terms of energy efficiency because it can be processed at a low temperature, and because it takes a small load on the equipment during product processing, the production can be increased.
[238]
In addition, the viscosity change data according to the change of the angular frequency in FIGS. 3 and 4 is the angular frequency ω to simulate the situation when the sample is injected at a high shear rate and when the sample is placed at a shear rate close to zero in a stationary state after injection. = Viscosity was measured in the range of 1-500 rad/s. This is to simulate such a situation that a certain amount of pressure is applied during polymer processing.
[239]
According to FIG. 3 , it can be confirmed that Example 2 has a lower complex viscosity than Comparative Example 7 in a specific frequency band set. In FIG. 4, even in the case of Example 3, it has a low complex viscosity in a specific frequency band set compared to Comparative Example 6. Therefore, it can be confirmed that the ethylene/alpha-olefin copolymer of the present invention has improved processability compared to the comparative example.
[240]
In other words, the ethylene/alpha-olefin copolymer prepared according to an embodiment of the present invention has significantly excellent processability through the fact that it exhibits a low complex viscosity under changing temperature conditions and changing shear rate conditions during processing. point can be seen.
[241]
[242]
As such, the ethylene/alpha-olefin copolymer of the present invention has a low density, low molecular weight and narrow molecular weight distribution, so it can be expected to have superior impact strength and mechanical properties compared to Comparative Examples. In addition, as the ethylene/alpha-olefin copolymers of Examples 1 to 5 exhibited a ReХRc value of 1.0 or less, more specifically, a ReХRc value of 0.95 or less, a comonomer such as 1-octene was uniformly distributed in the polymer. It shows structural stability. As a result, it can be seen that the reaction efficiency is improved through a uniform reaction when applied to the hot melt adhesive composition, and processability can be improved along with adhesiveness.
Claims
[Claim 1]
Ethylene/alpha-olefin copolymers satisfying the conditions of i) to iv) below: i) Density: 0.85 to 0.89 g/cc, ii) Molecular weight distribution (MWD): 1.5 to 3.0, iii) Viscosity: at 180°C temperature 6,000cP to 40,000cP when measured iv) ReХRc ≤ 1.0 In this case, Re=kee/kec, Rc=kcc/kce, and kee is the growth kinetic constant when ethylene is added to the growth chain whose terminal active point is an ethylene monomer. , kec represents the growth reaction rate when an alpha olefin comonomer is added to a growth chain having a terminal active point of an ethylene monomer, and kcc represents the growth reaction rate when an alpha olefin comonomer is added to a growth chain whose terminal active point is an alpha olefin comonomer represents the growth kinetics, and kce represents the growth kinetics constant when an ethylene monomer is added to the growth chain where the terminal active site is an alpha olefin comonomer.
[Claim 2]
The ethylene/alpha-olefin copolymer according to claim 1, wherein the viscosity is 8,500 to 35,000 cP as measured at a temperature of 180 °C.
[Claim 3]
The ethylene/alpha-olefin copolymer according to claim 1, wherein the weight average molecular weight is 17,000 to 40,000 g/mol.
[Claim 4]
The ethylene/alpha-olefin copolymer according to claim 1, wherein the ReХRc value is 0.95 or less.
[Claim 5]
The ethylene/alpha-olefin copolymer according to claim 1, wherein the ethylene/alpha-olefin copolymer has a density of 0.860 to 0.885 g/cc.
[Claim 6]
According to claim 1, wherein the alpha-olefin is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, An ethylene/alpha-olefin copolymer comprising at least one selected from the group consisting of 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene.
[Claim 7]
The ethylene/alpha-olefin copolymer according to claim 1, wherein the alpha-olefin is at least one selected from the group consisting of 1-butene, 1-hexene and 1-octene.
[Claim 8]
The ethylene/alpha-olefin copolymer according to claim 1, wherein the alpha-olefin is included in an amount of greater than 0 and 99 mol% or less based on the total weight of the copolymer.
[Claim 9]
The ethylene/alpha-olefin copolymer according to claim 1, further satisfying the following conditions v) to vii): v) the total number of unsaturated functional groups per 1,000 carbon atoms: 0.8 or less, vi) a number average molecular weight (Mn): 9,000 to 25,000, and vii) Melt Index (MI) at 190° C., 2.16 kg load according to ASTM D1238: 200 to 1,300 dg/min.