Title of the invention: Ethylene/alpha-olefin copolymer and its manufacturing method
Technical field
[One]
Mutual citation with related applications
[2]
This application claims the benefit of priority based on the Korean patent application 2018-0052045 filed May 4, 2018, and all contents disclosed in the literature of the Korean patent applications are incorporated as part of this specification.
[3]
[4]
Technical field
[5]
The present invention relates to an ethylene/alpha-olefin copolymer exhibiting excellent physical properties by having a small number of unsaturated functional groups 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 catalysts have been widely applied to conventional commercial processes since their invention in the 50s, but since they are multi-site catalysts with multiple active points, they are characterized by a wide molecular weight distribution of polymers. There is a problem in that there is a limit to securing desired physical properties because the composition distribution of is not uniform.
[7]
On the other hand, the metallocene catalyst is composed of a combination of a main catalyst composed of a transition metal compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum. Such a catalyst is a homogeneous complex catalyst and is a single site catalyst. A polymer having a narrow molecular weight distribution and a uniform composition distribution of a comonomer is obtained according to the single active point characteristics.According to the modification of the ligand structure of the catalyst and the change of polymerization conditions, the stereoregularity, copolymerization characteristics, molecular weight, and It has properties that can change crystallinity and the like.
[8]
U.S. Patent No. 5,914,289 describes a method of controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but it takes a lot of time and the amount of solvent used to prepare the supported catalyst. In addition, there was a hassle of having to support each of the metallocene catalysts used on the carrier.
[9]
Korean Patent Application No. 10-2003-0012308 discloses a method of controlling the molecular weight distribution by supporting a double-nuclear metallocene catalyst and a single-nuclear metallocene catalyst on a carrier together with an activator to change the combination of catalysts in the reactor and polymerization Is being disclosed. However, this method has a limitation in realizing the characteristics of each catalyst at the same time, and also has a disadvantage in that the metallocene catalyst portion is released from the carrier component of the completed catalyst, causing fouling in the reactor.
[10]
On the other hand, linear low-density polyethylene is a resin prepared by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, and thus has a narrow molecular weight distribution, short chain branches of a certain length, and no long chain branches. Linear low-density polyethylene film has high breaking strength and elongation as well as the properties of general polyethylene, and has excellent tear strength and drop impact strength, so its use in stretch films and overlap films, which are difficult to apply to existing low-density polyethylene or high-density polyethylene, is increasing. Are doing.
[11]
However, linear low-density polyethylene using 1-butene or 1-hexene as a comonomer is mostly manufactured in a single gas phase reactor or a single loop slurry reactor, and has higher productivity compared to the process using 1-octene comonomer, but these products are also used. Due to the limitations of catalyst technology and process technology, physical properties are significantly inferior to when using 1-octene comonomer, and the molecular weight distribution is narrow, resulting in poor processability.
[12]
U.S. Patent No. 4,935,474 reports on a method for preparing polyethylene having a broad molecular weight distribution by using two or more metallocene compounds. U.S. Patent No. 6,828,394 reports on a method for producing polyethylene having good processability and particularly suitable for films by mixing those having good comonomer binding properties and those not having good comonomer binding properties. In addition, U.S. Patent No. 6,841,631 and U.S. Patent No. 6,894,128 disclose a metallocene catalyst in which at least two kinds of metal compounds are used to prepare polyethylene having a bimodal or polymorphic molecular weight distribution, so that it can be used in films, blow molding, pipes, etc. It is reported that it is applicable. However, these products have improved processability, but the dispersion state of each molecular weight within the unit particles is not uniform, so the extrusion appearance is rough and physical properties are not stable even under relatively good extrusion conditions.
[13]
Against this background, there is a constant demand for production of better products with a balance between physical properties and processability, and in particular, the need for polyethylene copolymers having excellent physical properties, such as long-term properties, is further required.
Detailed description of the invention
Technical challenge
[14]
Accordingly, the present invention is to solve the problems of the prior art, and has a narrow molecular weight distribution, a small number of unsaturated functional groups and a R vd value, and thus excellent physical properties, particularly, low viscosity change rate even after long-term storage, excellent long-term physical properties. It is intended to provide an ethylene/alpha-olefin copolymer having low discoloration at high temperature and excellent high temperature stability and a method for producing the same.
[15]
In addition, the present invention is to provide a hot melt adhesive composition including the ethylene/alpha olefin copolymer and exhibiting excellent long-term properties, high temperature stability, and adhesive properties.
Means of solving the task
[16]
In order to solve the above problems, according to an embodiment of the present invention, an ethylene/alpha-olefin copolymer satisfying the following conditions i) to iv) is provided:
[17]
i) Viscosity: 6,000cP to 40,000cP when measured at 180°C,
[18]
ii) molecular weight distribution (MWD): 1.5 to 3.0,
[19]
iii) Total number of unsaturated functional groups per 1,000 carbon atoms: 0.8 or less,
[20]
iv) R vd value according to Equation 1 below: 0.5 or less
[21]
[Equation 1]
[22]

[23]
(Vinyl, vinylene, and vinylidene in Equation 1 mean the number of functional groups per 1,000 carbon atoms measured through nuclear magnetic spectroscopy)
Effects of the Invention
[24]
The ethylene/alpha-olefin copolymer according to the present invention has a low density, ultra-low molecular weight, and a narrow molecular weight distribution, thus exhibiting excellent impact strength and mechanical properties. In addition, the ethylene/alpha-olefin copolymer according to the present invention has a small number of total unsaturated functional groups in the polymer and a low vinylidene ratio, so that it can exhibit excellent long-term properties due to a small rate of change in viscosity over time, and has less discoloration at high temperatures High temperature stability can be improved.
[25]
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 long-term properties, high temperature stability, and A hot melt adhesive composition having adhesive properties can be prepared.
Best mode for carrying out the invention
[26]
The terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise", "include" or "have" are intended to designate the existence of a feature, step, component, or a combination of the implemented features, one or more other features or steps, It is to be understood that the possibility of the presence or addition of components, or combinations thereof, is not excluded in advance.
[27]
The present invention will be described in detail below and exemplifying specific embodiments, which can be made various changes and have various forms. However, this is not intended to limit the present invention to a specific form disclosed, it is to be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.
[28]
[29]
1. Ethylene/alpha-olefin copolymer
[30]
Hereinafter, the ethylene/alpha-olefin copolymer of the present invention will be described in detail.
[31]
The ethylene/alpha-olefin copolymer according to an embodiment of the present invention satisfies the following conditions i) to iv):
[32]
i) Viscosity: 4,000cP to 50,000cP when measured at 180°C,
[33]
ii) molecular weight distribution (MWD): 1.5 to 3.0,
[34]
iii) Total number of unsaturated functional groups per 1,000 carbon atoms: 0.8 or less,
[35]
iv) Rvd value according to Equation 1 below: 0.5 or less
[36]
[Equation 1]
[37]

[38]
(Vinyl, vinylene, and vinylidene in Equation 1 refer to the number of functional groups per 1000 carbon atoms measured through nuclear magnetic spectroscopy)
[39]
[40]
Cross-linking between copolymers is caused by vinyl and vinylidene containing double bonds, and the ethylene/alpha-olefin copolymer according to the embodiment is introduced with an optimized amount of hydrogen together with a catalyst to be described later during polymerization, The number of unsaturated functional groups in the copolymer, in particular the ratio of vinylidene, can be reduced, and in particular, by satisfying the above-described number of unsaturated functional groups and the conditions of R vd , it exhibits excellent high temperature stability with small discoloration, molecular weight and viscosity change rate even at high temperatures I can.
[41]
[42]
The ethylene/alpha-olefin copolymer according to an embodiment of the present invention has a viscosity measured at 180° C. of 50,000 cP or less under conditions that satisfy 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, and may be 4,000 cP or more, or 6,000 cP or more, or 7,000 cP or more, or 8,500 cP or more.
[43]
Specifically, in the ethylene/alpha-olefin copolymer according to the embodiment, the number of unsaturated functional groups including vinyl, vinylene, and vinylidene in the copolymer may be 0.8 or less per 1000 carbon atoms, and more specifically 0.6 or less, or 0.5 or less, or 0.45 or less, or 0.40 or less, and may be 0.1 or more, or 0.2 or more, or 0.23 or more.
[44]
In addition, the ethylene/alpha-olefin copolymer according to the embodiment has an R vd value of 0.5 or less calculated according to Equation 1 , more specifically 0.3 or less, or 0.25 or less, or 0.22 or less, and greater than 0 , Or 0.1 or more, or 0.15 or more.
[45]
In the present invention, the content (or number) of vinyl, vinylene, and vinylidene as unsaturated functional groups in the copolymer can be calculated from the results of nuclear magnetic resonance (NMR) analysis. Specifically, after dissolving the copolymer in a chloroform-d (w/TMS) solution, an Agilent 500MHz NMR device was used to measure the acquisition time of 2 seconds at room temperature and 16 times with a pulse angle of 45°. Corrected to 0 ppm, 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 CH 3 peak integral value was corrected to 3. The content can be calculated, and the number of each can be calculated based on the integral values ​​of vinyl, vinylene, and vinylidene in the 4.5-6.0 ppm range.
[46]
In addition, when two or more kinds of monomers are usually polymerized, the molecular weight distribution (MWD) increases, and as a result, impact strength and mechanical properties decrease, and a blocking phenomenon occurs. On the other hand, in the present invention, when an optimum amount of hydrogen is added during the polymerization reaction, the molecular weight and molecular weight distribution of the ethylene/alpha-olefin copolymer to be produced is reduced, and as a result, impact strength and mechanical properties can be improved.
[47]
[48]
In addition, the ethylene/alpha-olefin copolymer according to an embodiment of the present invention further has a density measured according to ASTM D-792 of 0.85 g/cc to 0.89 g under conditions that satisfy the physical property requirements as described above. May be /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.
[49]
In general, the density of olefin-based polymers is affected by the type and content of monomers used in polymerization, and the degree of polymerization, and in the case of copolymers, the influence is large by the content of comonomers. The olefin copolymer can be prepared, and the amount of comonomer that can be introduced into the copolymer can depend on the copolymerization of the catalyst, that is, the properties of the catalyst.
[50]
In the present invention, it is possible to introduce a large amount of comonomer by using a catalyst composition containing a transition metal compound having a specific structure. As a result, the ethylene/alpha-olefin copolymer according to an 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 preferably have a density of 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 density control The effect of maintaining mechanical properties and improving impact strength is more remarkable.
[51]
[52]
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, more specifically, 1.7 or more, or 1.8 or more, or 1.9 or more, 2.3 or less, or 2.1 or less, or 2.0 or less.
[53]
On the other hand, in the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are molecular weights in terms of polystyrene analyzed by gel permeation chromatography (GPC), and the molecular weight distribution is from the ratio of Mw/Mn. Can be calculated.
[54]
The ethylene/alpha-olefin copolymer according to an embodiment of the present invention may be an ultra-low molecular weight polymer 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.
[55]
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, 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).
[56]
When the weight average molecular weight and melt index satisfy the above range, it may be suitable for application to a hot-melt adhesive composition, and remarkable improvement in processability can be expected in association with viscosity. That is, the viscosity that affects the mechanical properties, impact strength, and processability of the ethylene/alpha-olefin copolymer can be controlled by adjusting the amount of catalyst used together with the type of catalyst used in the polymerization process, and in addition to the above conditions By meeting the viscosity range, it is possible to exhibit improved processability while maintaining excellent mechanical properties.
[57]
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.
[58]
[59]
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, and 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.
[60]
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.
[61]
In the present invention, the crystallization temperature and melting temperature of the ethylene/alpha-olefin copolymer can be measured using a Differential Scanning Calorimeter (DSC). Specifically, the copolymer is heated to 150° C., maintained for 5 minutes, and then lowered to 20° C., and the temperature is increased again. At this time, the rate of rise and fall of temperature are each adjusted to 10℃/min, and the result measured in the second temperature rising section is the melting temperature, and the result measured in the section appearing while decreasing the temperature is the crystallization temperature.
[62]
[63]
In addition, in the ethylene/alpha-olefin copolymer according to an embodiment of the present invention, the alpha-olefin monomer as a comonomer may be an olefin 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, 1-eicosene, and the like, and one of them alone or a mixture of two or more may be used.
[64]
Among these, the alpha-olefin monomer may be 1-butene, 1-hexene, or 1-octene, and most preferably 1-octene when considering the remarkable improvement effect when applied to a hot melt adhesive composition.
[65]
In addition, in the ethylene/alpha-olefin copolymer, the content of alpha-olefin, which is the comonomer, may be appropriately selected within a range that satisfies the above-described physical property requirements, and specifically, more than 0 and not more than 99 mol%, or It may be 10 to 50 mol%.
[66]
[67]
The ethylene/alpha-olefin copolymer according to another embodiment of the present invention satisfies the conditions of i) to vii) below.
[68]
i) Viscosity: 4,000cP to 50,000cP when measured at 180°C,
[69]
ii) density: 0.85 to 0.89 g/cc,
[70]
iii) molecular weight distribution (MWD): 1.5 to 3.0,
[71]
iv) Total number of unsaturated functional groups per 1000 carbon atoms: 0.8 or less,
[72]
v) Number average molecular weight (Mn): 9,000 to 25,000,
[73]
vi) Melt Index (MI) at 190° C., 2.16 kg load according to ASTM D1238: 200 to 1,300 dg/min, and
[74]
vii) Rvd value according to Equation 1 below: 0.5 or less
[75]
[Equation 1]
[76]

[77]
(Vinyl, vinylene, and vinylidene in Equation 1 refer to the number of functional groups per 1000 carbon atoms measured through nuclear magnetic spectroscopy)
[78]
[79]
2. Method for producing ethylene/alpha-olefin copolymer
[80]
Meanwhile, in the ethylene/alpha-olefin copolymer having the above physical properties, in the presence of a catalyst composition containing a transition metal compound of Formula 1, hydrogen is added at 45 to 100 cc/min to obtain ethylene and alpha-olefins. It can be prepared by a production method comprising the step of polymerizing the system monomer. Accordingly, according to another embodiment of the present invention, there is provided a method for preparing the ethylene/alpha-olefin copolymer described above:
[81]
[Formula 1]
[82]

[83]
In Formula 1,
[84]
R 1 is hydrogen; Alkyl of 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 of 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,
[85]
R 2a to R 2e are each independently hydrogen; halogen; Alkyl of 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,
[86]
R 3 is hydrogen; halogen; Alkyl of 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl of 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 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, and aryl having 6 to 20 carbon atoms ego,
[87]
R 4 to R 9 are each independently hydrogen; Silyl; Alkyl of 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl of 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with a hydrocarbyl having 1 to 20 carbon atoms; Two or more adjacent to each other among the R 6 to R 9 may be connected to each other to form a ring,
[88]
Q is Si or C,
[89]
M is a Group 4 transition metal,
[90]
X 1 and X 2 are each independently hydrogen; halogen; Alkyl of 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl of 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkylamino of 1 to 20 carbon atoms; Or arylamino having 6 to 20 carbon atoms.
[91]
[92]
In the case of polymerizing ethylene and alpha-olefin-based comonomers with hydrogen by including a transition metal compound having the structure of Formula 1 in the catalyst composition as described above, an ethylene/alpha-olefin copolymer having a low density and an ultra-low molecular weight as described above In this ethylene/alpha-olefin copolymer, the total number of unsaturated functional groups per 1,000 carbons is 0.8 or less, and the R vd value satisfies a value of 0.5 or less, so that discoloration, molecular weight and viscosity change rate are small, excellent It can exhibit high temperature stability.
[93]
That is, the crosslinking reaction that can be generated by the unsaturated functional group and the alkyl radical in the copolymer is dominant in vinyl or vinylidene with relatively little steric hindrance among the unsaturated functional groups, and when the crosslinking reaction proceeds, the viscosity can change greatly and the processability is adversely affected. There is a concern that it may lead to a decrease in stability at high temperature. However, by applying the manufacturing method according to an embodiment of the present invention, the ratio of the vinylidene content among the unsaturated functional groups can be reduced, and accordingly, the crosslinking reaction does not occur, and in the end, a copolymer having a low viscosity change rate at high temperature can be implemented. will be.
[94]
[95]
The substituents in Formula 1 will be described in more detail as follows.
[96]
R 1 is hydrogen; Alkyl of 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl of 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.
[97]
Specifically, R 1 is hydrogen; Alkyl of 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Aryl of 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]
More specifically, R 1 may be hydrogen or alkyl having 1 to 12 carbon atoms.
[99]
R 2a to R 2e are each independently hydrogen; halogen; Alkyl of 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.
[100]
Specifically, R 2a to R 2e are each independently hydrogen; halogen; Alkyl of 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.
[101]
More specifically, R 2a to R 2e are each independently hydrogen; Alkyl of 1 to 12 carbon atoms; Or it may be alkoxy having 1 to 12 carbon atoms.
[102]
R 3 is hydrogen; halogen; Alkyl of 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Aryl of 6 to 20 carbon atoms; Alkylaryl having 7 to 13 carbon atoms; Arylalkyl of 7 to 13 carbon atoms; Alternatively, it may be a 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 and phenyl having 1 to 12 carbon atoms.
[103]
Specifically, R 3 is hydrogen; halogen; Alkyl of 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 of 7 to 13 carbon atoms; Phenyl; Or 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 substituted with one or more selected from the group consisting of phenyl,
[104]
More specifically, R 3 is hydrogen; Alkyl of 1 to 12 carbon atoms; Or phenyl.
[105]
Each of R 4 to R 9 is independently hydrogen; Alkyl of 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Aryl of 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.
[106]
Specifically, the R 4 to R 9 are each independently hydrogen; Alkyl of 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Aryl of 6 to 12 carbon atoms; Alkylaryl having 7 to 13 carbon atoms; Or it may be an arylalkyl having 7 to 13 carbon atoms.
[107]
More specifically, R 4 and R 5 are each independently hydrogen; Or it may be a C1-C12 alkyl,
[108]
Two or more adjacent to each other among the 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.
[109]
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.
[110]
More specifically, R 6 to R 9 may each independently be hydrogen or methyl.
[111]
In addition, Q may be Si, and M may be Ti.
[112]
X 1 and X 2 are each independently hydrogen; halogen; Alkyl of 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Aryl of 6 to 12 carbon atoms; Alkylaryl having 7 to 13 carbon atoms; Arylalkyl of 7 to 13 carbon atoms; Alkylamino of 1 to 13 carbon atoms; Or it may be arylamino having 6 to 12 carbon atoms.
[113]
Specifically, X 1 and X 2 are each independently hydrogen; halogen; An alkyl group having 1 to 12 carbon atoms; Or it may be an alkenyl having 2 to 12 carbon atoms.
[114]
More specifically, X 1 and X 2 may each independently be hydrogen or alkyl having 1 to 12 carbon atoms.
[115]
[116]
In the transition metal compound of Formula 1, cyclopentadiene in which benzothiophene is fused by a cyclic bond, and an amido group (NR 1 ) are stably crosslinked by Q (Si, C, N or P), Group 4 transition metals form a coordinated bonded structure. When applied to olefin polymerization using the catalyst composition, it is possible to produce a polyolefin having characteristics such as high activity, high molecular weight, and high copolymerizability even at a high polymerization temperature.
[117]
Furthermore, the transition metal compound of Formula 1 has a structure in which a substituted or unsubstituted phenyl group is bonded to Q when an amido group (NR 1 ) is crosslinked by Q(Si, C), so that it is more stably crosslinked. It can be, and can have excellent electronic stability when coordinated with a transition metal.
[118]
In the case of a transition metal compound having such a structure, since the copolymerization is excellent due to the phenyl group, a low-density copolymer can be prepared 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 of being able to stably introduce hydrogen as well as high-temperature polymerization due to excellent molecular weight level.
[119]
That is, in the present invention, the above-described transition metal compound is used, but by introducing hydrogen in an optimized amount during the polymerization reaction, an ethylene/alpha-olefin copolymer having a narrow molecular weight distribution and a uniform comonomer distribution with an ultra-low molecular weight is provided. In addition, due to the electronic/structural stability of the transition metal compound, the incorporation of hydrogen is advantageous, and a homogeneous termination reaction by hydrogen occurs in the polymerization reaction to prepare an ultra-low molecular weight copolymer having a narrow molecular weight distribution. You can expect a good effect.
[120]
[121]
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.
[122]
[Formula 1-1] [Formula 1-2] [Formula 1-3]
[123]

[124]
[Formula 1-4] [Formula 1-5] [Formula 1-6]
[125]

[126]
[Formula 1-7] [Formula 1-8]
[127]

[128]
[Formula 1-9] [Formula 1-10]
[129]

[130]
[131]
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.
[132]
The cocatalyst is an organometallic compound containing a Group 13 metal, and specifically, may include at least one of a compound of the following formula 2, a compound of the following formula 3, and a compound of the following formula 4.
[133]
[Formula 2]
[134]
R 41 -[Al(R 42 )-O] n -R 43
[135]
In Formula 2,
[136]
R 41 , R 42 and R 43 are each independently 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,
[137]
n is an integer of 2 or more,
[138]
[Chemical Formula 3]
[139]
D(R 44 ) 3
[140]
In Formula 3, D is aluminum or boron,
[141]
R 44 is each independently a halogen, a C 1 to C 20 hydrocarbyl group, and a halogen substituted C 1 to C 20 hydrocarbyl any one of,
[142]
[Formula 4]
[143]
[LH] + [Z (A) 4 ] - or [L] + [Z (A) 4 ] -
[144]
In Chemical Formula 4,
[145]
L is a neutral or cationic Lewis base, H is a hydrogen atom,
[146]
Z is a Group 13 element, and A is each independently a hydrocarbyl group having 1 to 20 carbon atoms; A hydrocarbyloxy group having 1 to 20 carbon atoms; And at least one hydrogen atom of these substituents is any one of a substituent substituted with at least one of halogen, a C1-C20 hydrocarbyloxy group, and a C1-C20 hydrocarbylsilyl group.
[147]
[148]
More specifically, the compound of Formula 2 may be an alkylaluminoxane-based compound in which a repeating unit is bonded in a linear, circular or network type, and specific examples include methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane or tert-butylaluminoxane, and the like.
[149]
In addition, specific examples of the compound of Formula 3 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclo Pentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide , Trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron or tributyl boron, and the like, and may be particularly selected from trimethyl aluminum, triethyl aluminum or triisobutyl aluminum.
[150]
Further, examples of the compound of Formula 4 include a trisubstituted ammonium salt, a dialkyl ammonium salt, or a trisubstituted phosphonium salt type borate-based compound. 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-trimethylaninium)tetraphenylborate, Trimethylammonium tetrakis(pentafluorophenyl)borate, methylditetradecylammonium tetrakis(pentaphenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium, tetrakis(pentafluoro Phenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) ) Borate, N,N-dimethylaninium tetrakis (pentafluorophenyl) borate, N,N-diethylaninium tetrakis (pentafluorophenyl) borate, N,N-dimethyl (2,4,6- Trimethylaninium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (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-trimethylanil) Borate compounds in the form of trisubstituted ammonium salts such as nium) tetrakis-(2,3,4,6-tetrafluorophenyl)borate; Dialkyl ammonium salt form such as dioctadecyl ammonium tetrakis (pentafluorophenyl) borate, ditetradecyl ammonium tetrakis (pentafluorophenyl) borate or dicyclohexyl ammonium tetrakis (pentafluorophenyl) borate. compound; Or triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate or tri(2,6-, dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) ) Borate compounds in the form of a trisubstituted phosphonium salt such as borate.
[151]
By using such a cocatalyst, the molecular weight distribution of the finally produced ethylene/alpha-olefin copolymer becomes more uniform, and polymerization activity may be improved.
[152]
The cocatalyst may be used in an appropriate amount so that the activation of the transition metal compound of Formula 1 is sufficiently performed.
[153]
[154]
In addition, the catalyst composition may include the transition metal compound of Formula 1 supported on a carrier.
[155]
When the transition metal compound of Formula 1 is supported on a 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 the weight ratio within the above range, the optimum 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 weight ratio, it is possible to improve the catalytic activity and optimize the microstructure of the polymer to be produced.
[156]
Meanwhile, silica, alumina, magnesia, or a mixture thereof may be used as the carrier, or by drying these materials at a high temperature to remove moisture from the surface, the surface contains a highly reactive hydroxyl group or a siloxane group. It can also be used. In addition, the high-temperature dried carriers may further include oxides, carbonates, sulfates, or nitrate components such as Na 2 O, K 2 CO 3 , BaSO 4 and Mg(NO 3 ) 2 .
[157]
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°C, there is too much moisture so that the moisture on the surface and the cocatalyst react, and when it exceeds 800°C, the pores on the surface of the carrier are combined and the surface area decreases. It is not preferable because it disappears and only siloxane groups remain, and the reaction site with the cocatalyst decreases.
[158]
In addition, the amount of hydroxy groups on the surface of the carrier is preferably 0.1 to 10 mmol/g, and more preferably 0.5 to 5 mmol/g. The amount of hydroxy groups on the surface of the carrier can be controlled by a method and conditions for preparing the carrier or drying conditions such as temperature, time, vacuum or spray drying.
[159]
[160]
Meanwhile, the polymerization reaction of the ethylene/alpha-olefin copolymer may be carried out by continuously adding hydrogen in the presence of the above-described catalyst composition and continuously polymerizing ethylene and alpha-olefin-based monomers.
[161]
At this time, the hydrogen gas serves to suppress the rapid reaction of the transition metal compound at the initial stage of polymerization and terminate the polymerization reaction. Accordingly, by controlling the use and amount of hydrogen gas, an ethylene/alpha-olefin copolymer having a narrow molecular weight distribution with an ultra-low molecular weight can be effectively prepared.
[162]
The hydrogen gas may be added at 45 to 100 cc/min, more specifically 50 to 95 cc/min. When introduced under the above conditions, the produced ethylene/alpha-olefin polymer can implement the physical properties in the present invention. If the content of hydrogen gas is less than 45 cc/min, termination of the polymerization reaction does not occur uniformly, making it difficult to prepare an ethylene/alpha-olefin copolymer having the desired physical properties, and also exceeding 100 cc/min. In this case, there is a concern that a termination reaction occurs too quickly, resulting in an ethylene/alpha-olefin copolymer having an excessively low molecular weight.
[163]
[164]
In addition, the polymerization reaction may be carried out at 80 to 200°C, but the number of unsaturated functional groups in the ethylene/alpha-olefin copolymer can be more easily controlled by controlling the polymerization temperature together with the amount of hydrogen added. Accordingly, in detail, the polymerization reaction may be 100 to 150°C, more specifically 100 to 140°C.
[165]
[166]
In addition, during the polymerization reaction, an organic aluminum compound for removing moisture in the reactor is further added, so that the polymerization reaction may proceed in the presence of the organic aluminum compound. Specific examples of such organoaluminum compounds include trialkyl aluminum, 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 3H 9 ) 2 AlCl or (C 2 H 5 ) 3 A l2 Cl 3 , and the like. These organoaluminum compounds may be continuously introduced into the reactor, and may be added in a ratio of about 0.1 to 10 moles per 1 kg of the reaction medium introduced into the reactor for proper moisture removal.
[167]
In addition, the polymerization pressure may be about 1 to about 100 Kgf/cm 2 , preferably about 1 to about 50 Kgf/cm 2 , more preferably about 5 to about 30 Kgf/cm 2 .
[168]
In addition, when a transition metal compound is used in the form supported on a carrier, the transition metal compound is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, such as 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 after removing a small amount of water or air acting as a catalyst poison by treating a small amount of alkyl aluminum, and it is possible to further use a cocatalyst.
[169]
The ethylene/alpha-olefin copolymer prepared by the above-described production method has an ultra-low molecular weight and a narrow molecular weight distribution, and at the same time, the vinyl content in the polymer is minimized, and R vd satisfies the conditions of 0.5 or less. Accordingly, excellent physical properties, particularly high temperature stability, can be exhibited, and when applied to a hot melt adhesive composition, adhesive properties and processability can be improved.
[170]
[171]
Accordingly, according to another embodiment of the present invention, there is provided a hot melt adhesive composition comprising the ethylene / alpha-olefin copolymer described above.
[172]
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.
Mode for carrying out the invention
[173]
Example
[174]
Hereinafter, preferred embodiments are presented to aid in understanding the present invention. However, the following examples are only provided to more easily understand the present invention, thereby not limiting the content of the present invention.
[175]
[176]
[Synthesis Example: Preparation of transition metal compound]
[177]
Step 1: Preparation of Ligand Compound (1a-1)
[178]
In a 250 mL Schlenk flask, 1, 2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene 10 g (1.0 eq, 49.925 mmol) and THF 100 mL were added, 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, and then stirred at room temperature overnight. After stirring, vacuum drying, and then extracted with 100 mL of hexane.
[179]
T-BuNH in 100 mL of the 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, vacuum drying, and then extracted with 150 mL of hexane. After drying the solvent, 13.36 g (68%, dr = 1:1) of a yellow solid was obtained.
[180]
(1a-1)
[181]

[182]
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)
[183]
[184]
Step 2: Preparation of transition metal compound (1a)
[185]
In a 100 mL Schlenk flask, 4.93 g (12.575 mmol, 1.0 eq) of the ligand compound of Formula 2-4 and 50 mL (0.2M) of toluene were added, and 10.3 mL (25.779 mmol, 2.05 eq, 2.5M in hexane) of n-BuLi was added. Was added dropwise at -30°C, followed by stirring at room temperature overnight. After stirring, MeMgBr 12.6 mL (37.725 mmol, 3.0 eq, 3.0 M in diethyl ether) was added dropwise, and then TiCl 4 13.2 mL (13.204 mmol, 1.05 eq, 1.0 M in toluene) was sequentially added and stirred at room temperature overnight. . After stirring, vacuum-dried, and extracted with 150 mL of hexane, and after removing the solvent to 50 mL, 4 mL (37.725 mmol, 3.0eq) of DME was added dropwise, followed by stirring at room temperature overnight. After vacuum drying again, it was extracted with 150 mL of hexane. After drying the solvent, 2.23 g (38%, dr = 1:0.5) of a brown solid was obtained.
[186]
(1a)
[187]

[188]
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)
[189]
[190]
[Production of ethylene/alpha-olefin copolymer]
[191]
Example 1
[192]
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 Synthesis Example above 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 and maintained at a pressure of 89 bar and a polymerization temperature of 125° C. for 60 minutes or longer, and the copolymerization reaction was continuously performed to obtain a copolymer. Was prepared.
[193]
Next, the remaining ethylene gas was removed, and the resulting copolymer-containing solution was dried in a vacuum oven for 12 hours or longer, and then physical properties of the obtained copolymer were measured.
[194]
[195]
Examples 2 to 5, and Comparative Examples 1 to 7
[196]
A polymer was prepared in the same manner as in Example 1, except that reactants were added in the amounts shown in Table 1 below.
[197]
[Table 1]
Catalyst input amount (μmol/min) Cocatalyst input amount (μmol/min) 1-C8 input (kg/h) TiBAl(mmol/min) Polymerization temperature (℃) H 2 input amount (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
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
[198]
* In Comparative Examples 6 and 7, [Me 2 Si(Me 4 C 5 )NtBu]Ti(CH 3 ) 2 was used as a catalyst.
[199]
[200]
[Evaluation of physical properties of olefin polymer]
[201]
Experimental Example 1
[202]
The physical properties of the ethylene/alpha-olefin copolymer prepared in Examples and Comparative Examples were measured by the following method, and are shown in Table 2.
[203]
1) Density (Density, g/cm 3 ): It was measured according to ASTM D-792.
[204]
2) Viscosity (cP) : It was measured according to the following method using a Brookfield RVDV3T viscometer. Specifically, a sample is placed in a 13ml sample chamber, heated to 180°C using a Brookfield Thermosel, and when the sample is completely dissolved, lower the viscometer device to fix the spindle in the sample chamber, and the spindle (SC-29 hot-melt spindle ) Was fixed at 20 rpm, read for more than 20 minutes or until the value stabilized, and the final value was recorded.
[205]
3) Viscosity change rate (%) : It was measured according to the following method using a Brookfield RVDV3T viscometer. Specifically, a sample is placed in a 13ml sample chamber, heated to 180°C using a Brookfield Thermosel, and when the sample is completely dissolved, lower the viscometer device to fix the spindle to the sample chamber, and the spindle (SC-29 hot-melt spindle After fixing the rotation speed of) at 20 rpm, the value was recorded once per hour for 72 hours. The viscosity change rate was calculated by converting the difference between the initial viscosity and the viscosity after 72 hours into a percentage.
[206]
4) 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, and the temperature was lowered to -100° C. and then the temperature was increased again. At this time, the rate of rise and fall of the temperature were 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 rises.
[207]
5) Crystallization temperature (Tc, ℃) : It was carried out in the same manner as the melting temperature measurement using DSC, and the maximum point of the exothermic peak from the curve that appears while decreasing the temperature was taken as the crystallization temperature.
[208]
6) Weight average molecular weight (g/mol) and molecular weight distribution (MWD) : The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined under the following conditions using gel permeation chromatography (GPC: PL GPC220). Each was measured, and the weight average molecular weight was divided by the number average molecular weight to calculate the molecular weight distribution.
[209]
-Column: PL Olexis
[210]
-Solvent: Trichlorobenzene (TCB)
[211]
-Flow rate: 1.0 ml/min
[212]
-Sample concentration: 1.0 mg/ml
[213]
-Injection volume: 200 µl
[214]
-Column temperature: 160℃
[215]
-Detector: Agilent High Temperature RI detector
[216]
-Standard: Polystyrene (corrected by 3rd order function)
[217]
7) Total number of unsaturated functional groups (number/1000 C) : From the results of NMR analysis, the number of vinyl, vinylene, and vinylidene groups per 1000 carbons was measured.
[218]
Specifically, first, in order to remove residual 1-octene that may be present in the specimen, the polymer was prepared by reprecipitation 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 while stirring to re-precipitate the polymer, and then the re-precipitated polymer was vacuum-dried at room temperature. The above process was repeated once more to obtain a polymer from which residual 1-octene was removed.
[219]
30 mg of the sample of the polymer obtained above was dissolved in 1 ml of a chloroform-d (w/TMS) solution. Using an Agilent 500MHz NMR instrument, 16 measurements were made at room temperature with a acquisition time of 2 seconds and a pulse angle of 45°. In 1 H NMR, the TMS peak was corrected to 0 ppm, the CH 3 related peak of 1-octene at 0.88 ppm , and the CH 2 related peak of ethylene at 1.26 ppm (broad singlet). The content was calculated by correcting the CH 3 peak integral value to 3. The number of vinyl, vinylene, and vinylidene was calculated based on the integral value of each functional group in the 4.5-6.0 ppm range. For reference, Comparative Example 6 was not measured because the viscosity was too low.
[220]
[221]
8) R vd : R vd value was calculated according to Equation 1 below from the number of vinyl, vinylene, and vinylidene measured through the NMR analysis .
[222]
[Equation 1]
[223]

[224]
(In Equation 1, vinyl, vinylene, and vinylidene refer to the number of functional groups per 1000 carbon atoms measured through nuclear magnetic spectroscopy)
[225]
[Table 2]
Density(g/cc) Tc/Tm( o C) Viscosity (cP) Viscosity change rate (%) Number of unsaturated functional groups (pcs/1000C) R vd Mw Molecular weight distribution
Total content vinyl Vinylene Vinylidene
Example 1 0.873 50.6 / 66.5 35000 18 0.40 0.05 0.27 0.08 0.20 34900 1.98
Example 2 0.875 52.0 / 68.1 17000 15 0.35 0.04 0.24 0.07 0.20 24400 1.96
Example 3 0.876 52.3 / 68.9 13500 14 0.32 0.03 0.22 0.07 0.22 22400 1.98
Example 4 0.877 53.2 / 69.7 8500 11 0.29 0.03 0.20 0.06 0.21 19500 1.77
Example 5 0.875 52.2 / 68.3 17000 12 0.30 0.02 0.21 0.07 0.18 24500 1.96
Comparative Example 1 0.872 49.7 / 66.0 >50000 N/A 1.36 0.20 0.78 0.39 0.29 46800 2.14
Comparative Example 2 0.874 51.5 / 67.6 >50000 N/A 0.54 0.06 0.38 0.10 0.19 75400 2.08
Comparative Example 3 0.874 51.3 / 67.8 >50000 N/A 0.45 0.04 0.32 0.09 0.20 57700 2.09
Comparative Example 4 0.873 50.5 / 66.3 >50000 N/A 0.42 0.04 0.29 0.09 0.21 48700 2.08
Comparative Example 5 0.879 55.7 / 72.7 3500 N/A 0.29 - - - - 14600 1.97
Comparative Example 6 0.876 56.1 / 73.2 13900 22 0.32 0.03 0.10 0.20 0.63 22800 1.94
Comparative Example 7 0.875 55.3 / 73.1 15800 41 1.38 0.19 0.79 0.40 0.29 26700 2.24
[226]
In Table 2, "-" means not to be measured, and "N/A" means that measurement is impossible.
[227]
[228]
Referring to Table 2, the ethylene/alpha-olefin copolymers of Examples 1 to 5 prepared by using the catalyst composition containing a transition metal compound according to the present invention and adding hydrogen during polymerization reaction, are Comparative Examples 1 to 7 Compared with, it can be confirmed that it has a low density and at the same time an ultra-low molecular weight (evaluated by viscosity), a narrow molecular weight distribution, and a total number of unsaturated functional groups of 0.5 or less per 1,000 carbons, while at the same time having an R vd value of 0.5 or less, specifically 0.22 or less.
[229]
Specifically, in the case of Comparative Examples 1 to 4 in which hydrogen was not added or a certain amount or more was not added, a copolymer having a fairly high molecular weight was prepared, and it can be predicted that physical properties are poor due to a wide molecular weight distribution. In addition, because of its high viscosity, it was impossible to measure the viscosity and the rate of change thereof with the SC-29 high-temperature-melting spindle (5000 to 45000 cP), and thus it is not suitable for application to a hot melt adhesive composition. Further, in the case of Comparative Example 2, the value of R vd was similar to that of the Example, but the total number of unsaturated functional groups exceeded 0.5, so that physical properties were expected to decrease.
[230]
In addition, in the case of Comparative Example 5 in which too much hydrogen was added, polymerization was prematurely terminated by hydrogen, and a copolymer having a large molecular weight was produced, and the viscosity was low. It was impossible to measure the viscosity change rate.
[231]
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 relatively wide molecular weight distribution, and it was confirmed that the total number of unsaturated functional groups was equivalent to 1.38. In the case of the injected Comparative Example 6, the molecular weight distribution and viscosity characteristics were similar, and the total number of unsaturated functional groups was significantly reduced, but it can be seen that the R vd value was relatively increased.
[232]
This may be the effect of the compound used as a catalyst, and looking at the process of generating unsaturated functional groups from the viewpoint of beta-hydride elimination, vinylidene is produced when polymerization is terminated after 1,2-insertion of octene. When polymerization is terminated after -insertion, vinylene is produced, and when ethylene is inserted and terminated, vinyl is produced. If the copolymerization of the catalyst is excellent, 2,1-insertion is also increased, and accordingly, the content of vinylene increases and the content of vinylidene decreases.
[233]
That is, the transition metal compound used as the catalyst composition in Examples 1 to 5 had better copolymerizability than the catalysts used in Comparative Examples 6 and 7 and thus 2,1-insertion increased, and the content of vinylene increased. Although the content of vinylidene was reduced, in the case of Comparative Examples 6 and 7, it can be said that the result was not decreased.
[234]
In this regard, when looking at the viscosity change rate data, Comparative Example 7 had a relatively low vinylidene content ratio, but since the total content of the number of unsaturated functional groups such as vinyl and vinylidene was large, the viscosity change rate over time was large. Through this, it can be predicted that the stability at high temperature will also be poor.
[235]
On the other hand, in the case of the copolymers of Examples 1 to 4, the total content of the number of unsaturated functional groups is small compared to Comparative Example 7 and the ratio of vinylidene is low, so that the viscosity change rate is small. Is expected.
[236]
In addition, when comparing Example 3 and Comparative Example 6, in which the total number of unsaturated functional groups is equal to 0.32/1000C, the viscosity change rate of Example 3 having a low Rvd value is about twice that of Comparative Example 6 having a high Rvd value It can be seen that this is small.
[237]
Through this, it can be confirmed from the experimental data that the viscosity change is small only when the total content of the unsaturated functional groups as well as the Rvd value are also low.
Claims
[Claim 1]
Ethylene/alpha-olefin copolymer satisfying the conditions of the following i) to iv): i) Viscosity: 6,000 cP to 40,000 cP as measured at 180° C., ii) Molecular weight distribution (MWD): 1.5 to 3.0, iii) carbon Total number of unsaturated functional groups per 1,000 atoms: 0.8 or less, iv) R vd value according to Equation 1 below: 0.5 or less [Equation 1] (vinyl, vinylene, and vinyl in Equation 1 Vinylidene refers to the number of functional groups per 1000 carbon atoms measured through nuclear magnetic spectroscopy.)
[Claim 2]
The ethylene/alpha-olefin copolymer according to claim 1, wherein the density is 0.85 to 0.89 g/cc.
[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 viscosity is 8,500 to 35,000 cP as measured at 180°C.
[Claim 5]
The ethylene/alpha-olefin copolymer of claim 1, wherein the R vd value according to Equation 1 is 0.3 or less.
[Claim 6]
The method of 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, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene to the ethylene/alpha-olefin copolymer comprising at least one selected from the group consisting of.
[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 of claim 1, wherein the alpha-olefin is contained in an amount of more 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 meeting the following conditions v) to vii): v) Total number of unsaturated functional groups per 1000 carbon atoms: 0.8 or less, vi) number average molecular weight (Mn): 9,000 to 25,000, vii) Melt Index (MI) at 190° C., 2.16 kg load according to ASTM D1238: 200 to 1,300 dg/min.