KR20190081822A - Olefin polymer and preparation method thereof - Google Patents

Abstract

The present invention relates to an olefin polymer provided as an olefin monomer and olefin comonomer are copolymerized. The softening point of the olefin polymer is 80 to 120°C. The olefin polymer has different values of the first melting temperature and the second melting temperature. The olefin polymer comprises the melting temperature (Tm) in different ranges and has excellent thermal stability.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymer,

The present invention relates to olefinic polymers, and relates to olefinic polymers comprising a first melting temperature and a second melting temperature in different ranges, and a process for their preparation.

A metallocene catalyst, which is one of the catalysts used to polymerize olefins, is a compound in which a ligand such as a cyclopentadienyl group, an indenyl group or a cycloheptadienyl group is coordinated to a transition metal or a transition metal halide compound as a basic form .

It has been known that the olefin polymer polymerized using such a metallocene catalyst has a narrow molecular weight distribution (MWD) as compared with the olefin polymer polymerized by the conventional Ziegler-Natta catalyst, and has a constant comonomer distribution.

On the other hand, olefin polymers polymerized using a single metallocene catalyst generally have a single melting temperature (Tm), and thus have low thermal stability because the crystals melt and crystallize at specific temperatures only.

The problem to be solved by the present invention is to provide an olefin-based polymer containing different ranges of melting temperature (Tm) and having excellent thermal stability. It is another object of the present invention to provide an olefin polymer having a relatively low density and a high molecular weight, but having a high softening point.

The present invention has been made in view of the above problems, and it is an object of the present invention to provide a method of manufacturing the same.

The olefin polymer according to an embodiment of the present invention is formed by copolymerization of an olefin monomer and an olefin comonomer and has a softening point of 80 to 120 DEG C and has a first melting temperature and a second melting temperature Wherein the first melting temperature and the second melting temperature have different values.

The difference between the first melting temperature and the second melting temperature may be from 10 캜 to 80 캜.

Specifically, the first melting temperature is from -20 캜 to 80 캜, and the second melting temperature is from 80 캜 to 140 캜

The crystallinity of the olefin-based polymer may be from 2% to 20%.

Preferably, the total crystallinity of the olefinic polymer may be from 5% to 15%.

The ratio of the first crystallinity, which is the degree of crystallization to the first melting temperature, and the second degree of crystallinity, which is the crystallinity to the second melting temperature, may be from 99: 1 to 75:25.

The weight average molecular weight of the olefin-based polymer may be from 5,000 g / mol to 60,000 g / mol.

The molecular weight distribution of the olefin-based polymer may be 1.3 to 3.0.

The content of the comonomer of the olefin-based polymer may be 10 wt% to 50 wt%.

The olefin polymer may have a density of 0.860 g / cm 3 to 0.900 g / cm 3.

The olefin-based polymer may be formed by copolymerization under an olefin polymerization catalyst comprising a transition metal compound represented by the following formula (A-1).

≪ Formula (A-1) >

In the above formula (A-1), M is titanium (Ti), zirconium (Zr) or hafnium (Hf)

X is independently selected from the group consisting of halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkyl, amido, C _6-20 aryl or C _1-20 alkylidene amido and also, Q ₂ is carbon (C), silicon (Si), germanium (Ge) or tin (Sn ), Each of R ¹ to R ¹⁴ is independently hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, unsubstituted C _1-20 alkyl, C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _{3- 20} heteroaryl group, or a substituted or unsubstituted C _1-20 silyl group, at least two adjacent of R ¹ to R ¹² are connected to each other to form a substituted or unsubstituted C _4-20 ring.

Specifically, M is zirconium or hafnium, X is each independently halogen or C _1-20 alkyl, Q ₂ is carbon or silicon, and R ¹ to R ⁵ , R ⁷ to R ¹⁰ and R ¹² Are each hydrogen, and R ⁶ and R ¹¹ are each independently hydrogen, substituted or unsubstituted C _1-20 alkyl, or substituted or unsubstituted C _6-20 aryl, and each of R ¹³ to R ¹⁴ is independently , Or substituted or unsubstituted C _1-20 alkyl.

More specifically, the formula (A-1) may be represented by the following formula (A-2).

≪ Formula (A-2) >

Alternatively, the formula (A-1) may be represented by the following formula (A-3).

<A-3>

At least one of the olefin-based monomer and the olefin-based comonomer may include an alpha-olefin.

The olefin-based monomer and the olefin-based comonomer may be ethylene and 1-octene, respectively.

The adhesive according to another embodiment of the present invention includes the above olefin-based polymer.

The details of other embodiments are included in the detailed description and drawings.

The embodiments of the present invention have at least the following effects.

The olefinic polymers of the present invention contain different ranges of melting temperatures (Tm) and have excellent thermal stability.

In addition, the olefin polymer of the present invention satisfies low density and low molecular weight characteristics and high softening point characteristics at the same time and has excellent physical properties.

The effects according to the embodiments of the present invention are not limited by the contents exemplified above, and more various effects are included in the specification.

1 is a DSC curve of an ethylene / 1-octene copolymer synthesized in Production Example 1. FIG.
2 is a DSC curve of the ethylene / 1-octene copolymer synthesized in Production Example 2. Fig.
3 is a DSC curve of the ethylene / 1-octene copolymer synthesized in Production Example 3. Fig.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

The olefin-based polymer according to one embodiment of the present invention may be a polymer of an olefin-based monomer or a copolymer of an olefin-based monomer and a comonomer.

The olefinic monomer may be selected from the group consisting of C _2-20 alpha-olefins, C _1-20 diolefins, C _3-20 cyclo-olefins, and C _3-20 cyclodiolefins. And may be one or more selected from the group consisting of

In an exemplary embodiment, the olefinic monomer is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, , 1-dodecene, 1-tetradecene, 1-hexadecene, and the like, but are not limited thereto. The olefin-based polymer may be a homopolymer containing only one of the above-exemplified olefin-based monomers, or a copolymer containing two or more kinds of homopolymers. For example, the olefin-based polymer may be a copolymer in which ethylene and 1-octene are copolymerized.

The olefinic polymer according to one embodiment of the present invention may comprise a plurality of melt temperatures. When the olefinic polymer contains a plurality of melting temperatures, since the crystals melt and crystallize at a plurality of temperatures, they have high thermal stability and can exhibit excellent properties in a hot melt adhesive or the like.

In one embodiment, the olefinic polymer may comprise a first melting temperature and a second melting temperature. The second melting temperature may be higher than the first melting temperature. The difference between the second melting temperature and the first melting temperature may be from 10 캜 to 80 캜.

In a specific embodiment, the first melting temperature (Tm1) of the olefinic polymer may be in the range of -20 to 80 占 폚, and the second melting temperature (Tm2) may be in the range of 80 to 120. Preferably, the first melting temperature Tm1 is between 0 ° C and 80 ° C, and the second melting temperature Tm2 is between 80 ° C and 140 ° C. More preferably, the first melting temperature (Tm1) may be 30 to 80 占 폚, and the second melting temperature (Tm2) may be 90 to 120 占 폚, but the present invention is not limited thereto.

The olefin-based polymer may have a crystallinity of 2% to 20%. Preferably, it may have a degree of crystallinity of 5% to 15%.

The crystallinity can be calculated by measuring the melting heat (? H) in a DSC curve obtained from a differential scanning calorimeter (DSC) and substituting it into the following equation (1).

[Formula 1]

Crystallinity (%) = ΔH _measurement / ΔH _100% * 100

The heat of fusion (ΔH _measurement ) can be obtained by measuring the temperature () - flow (W / g) curve on the DSC curve and the area of the linear baseline for this curve. ΔH _100% is the measured theoretical melting enthalpy for a 100% crystalline olefinic polymer and is 290 J / g.

The crystallinity of the olefinic polymer has a close correlation with the solubility and adhesion performance of the olefinic polymer. When the degree of crystallinity of the olefin-based polymer is 4% or more, the copolymer can be easily produced, a crystal region of a certain level or higher can be secured, and the adhesion performance can be maintained. In addition, when the degree of crystallinity is 8% or more, excellent properties are exhibited in the pot life which is the time for curing of the adhesive. That is, the olefin-based polymer having a crystallinity of 8% or more has a short pot life and exhibits excellent properties in a hot melt adhesive or the like due to its high adhesive strength. The degree of crystallinity of the olefin-based polymer should be 13% or less so that the solubility of the olefin-based polymer in the solvent is high, which is advantageous in securing ease of manufacture.

The total crystallinity of the olefinic polymer may be calculated as the sum of the degree of crystallization at each melting temperature. For example, the olefinic polymer has a first crystallinity within a first melting temperature (Tm1) range and a second crystallinity within a second melting temperature (Tm2) range. In this case, the total crystallinity corresponds to the first crystallinity Can be calculated as the sum of the second crystallinity.

If the second melting temperature is higher than the first melting temperature, the first crystallization degree at the first melting temperature of a relatively low temperature may be larger than the second crystallization degree. In one embodiment, the first crystallinity may be between 3% and 15% when the first melting temperature (Tm1) is between -20 ° C and 80 ° C. And the second crystallization degree may be 0.05% to 0.7% when the second melting temperature is 80 ° C to 120 ° C.

The ratio of the first crystallinity to the second crystallinity may be, for example, from 1: 0.1 to 1: 0.25. In other words, the ratio of the first crystallinity to the second crystallinity of the olefinic polymer may be from 99: 1 to 80:20.

The olefin polymer may have a weight average molecular weight (Mw) of 5,000 g / mol to 60,000 g / mol and a molecular weight distribution (MWD) of the olefin polymer may be 1.3 to 3.0. The molecular weight distribution can be calculated by the following equation (2).

[Formula 2]

MWD = Mw / Mn

In the formula 2, Mn is a number-average molecular weight and Mw is a weight-average molecular weight.

When the weight average molecular weight of the olefin polymer is 60,000 g / mol or less, compatibility with other solvents is excellent. Specifically, for example, when the olefin-based polymer is used in a hot melt adhesive, it can be uniformly mixed with other constituents such as a tackifier resin, a wax, and the like.

The content of the comonomer of the olefin-based polymer may be 10 wt% to 50 wt%. The olefin-based polymer may have a density of 0.860 g / cm 3 to 0.900 g / cm 3.

Generally, as the content of the comonomer increases, the density of the olefin polymer decreases, and the side branch ratio increases, thereby increasing the adhesion. However, if the content of the comonomer is excessively high, the crystallinity of the polymer is deteriorated and the proportion of the polymer present in the amorphous state increases, so that the solidification of the polymer may be difficult. When the content of the comonomer is 10 wt% to 50 wt%, excellent adhesion can be secured while maintaining the fluidity of the olefin-based polymer.

The softening point of the olefin-based polymer may be 80 ° C to 120 ° C. When the softening point of the olefinic polymer is 80 DEG C or higher, the olefin polymer is not softened in an environment where it can be generally placed, and thus the application range is widened. On the other hand, when the softening point is too high, the olefinic polymer must be provided with a high temperature for processing, resulting in poor processability and pot life. From this viewpoint, the softening point of the olefin-based polymer may be 120 DEG C or less.

The present invention provides an adhesive produced using the olefinic polymer described above according to another embodiment. In an exemplary embodiment, the olefinic polymer described above may be made from a hot melt adhesive.

As described above, since the olefin-based polymer of the present invention has a plurality of melting points and satisfies an appropriate total crystallinity and density range, the hot-melt adhesive containing the olefin-based polymer has excellent adhesion, .

Hereinafter, a method for producing an olefin-based polymer according to an embodiment of the present invention will be described.

The olefinic polymer according to one embodiment of the present invention comprises polymerizing the olefin monomers under the catalyst for olefin polymerization. The olefin monomers can be selected, for example, from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, , 1 -dodecene, 1-tetradecene, 1-hexadecene, and the like, and the olefin polymer may be a homopolymer or a copolymer.

The olefin-based polymer can be produced by gas phase polymerization, solution polymerization, slurry polymerization or the like, for example. When the olefin polymer is prepared by the solution polymerization method or the slurry polymerization method, examples of the solvent to be used include C _5-12 aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane and isomers thereof; Aromatic hydrocarbon solvents such as toluene and benzene; Hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene; And mixtures thereof. However, the present invention is not limited to these.

Generally, olefinic polymers having a plurality of melting temperatures can be synthesized using a hybrid catalyst comprising a plurality of catalysts. However, since it is difficult to predict and control the activity and the copolymerization of each of the mixed catalysts, it is difficult to prepare an olefin polymer having properties suitable for the application, and the two or more catalyst components are not uniformly mixed , Quality control is not easy.

Accordingly, the method for producing an olefin-based polymer according to one embodiment synthesizes an olefin polymer using a single catalyst. Although it is common for a polymer to be synthesized using a single catalyst to have a single melting temperature, a transition metal compound represented by the following formula (A-1) may exhibit a melting temperature of 2 or more in the olefin polymer .

&Lt; Formula (A-1) >

In the above formula (A-1)

M is a Group 4 transition metal, and may be titanium (Ti), zirconium (Zr) or hafnium (Hf). In one embodiment, M may be zirconium.

X is independently selected from the group consisting of halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkyl, amido, may indenyl C _6-20 aryl or C _1-20 amido alkali. In one embodiment, X may be C _1-6 alkyl.

Each Q may independently be carbon (C), silicon (Si), germanium (Ge), or tin (Sn). For example, Q may be carbon.

R ¹ to R ¹⁴ each represent hydrogen, independently substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted Substituted or unsubstituted C _1-6 alkyl, C _1-20 alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl , A substituted or unsubstituted C _1-20 alkylamido, a substituted or unsubstituted C _6-20 arylamido, a substituted or unsubstituted C _1-20 alkylidene, or a substituted or unsubstituted C _1-20 silyl Lt; / RTI &gt; Further, each of R ¹ to R ¹² may be independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring.

In an exemplary embodiment, the transition metal compound represented by the above formula (A-1) may be a compound represented by the following formula A-2 or a compound represented by the following formula (A-3) But are not limited to compounds.

<A-2>

<A-3>

The olefin polymerization catalyst composition of the present invention may further comprise a cocatalyst compound.

The cocatalyst compound may include at least one of a compound represented by the formula (1), a compound represented by the formula (2), and a compound represented by the formula (3).

&Lt; Formula 1 >

In Formula 1, n is an integer of 2 or more, and R _a may be a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen. Specifically, R _a may be methyl, ethyl, n-butyl or isobutyl, but is not limited thereto.

(2)

R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, a C _1-20 hydrocarbon group substituted with halogen, or a group represented by the formula A C _1-20 alkoxy group. Specifically, when D is aluminum, R _b , R _c and R _d may each independently be methyl or isobutyl, and when D is boron, R _b , R _c and R _d are each pentafluoro Phenyl, but is not limited thereto.

(3)

^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -

Wherein L is a neutral or cationic Lewis base, [LH] ⁺ or [L] ⁺ is a Bronsted acid, Z is a Group 13 element, and A is independently a substituted or unsubstituted C _{6- 20} aryl group or a substituted or unsubstituted C _1-20 alkyl group. Specifically, the [LH] ⁺ may be a dimethylanilinium cation dimethyl, wherein [Z (A) _4] ^- is _{[B (C 6 F 5)} 4] - can be a, the [L] ⁺ is [( C ₆ H ₅ ) ₃ C] ⁺ , but is not limited thereto.

The olefin polymerization catalyst of the present invention may further comprise a transition metal compound, and a carrier carrying the cocatalyst compound.

The carrier may include a substance containing a hydroxyl group on its surface, and preferably a material having a hydroxyl group and a siloxane group having high reactivity and dried on the surface and having moisture removed may be used. Silica-alumina, silica-magnesia, and the like, which are usually dried at high temperature, and which are usually made of oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ , Sulfate, and nitrate components. Or carbon, zeolite, magnesium chloride, and the like. However, it is not limited thereto, and it is not particularly limited as long as it can support the transition metal compound and the cocatalyst compound.

As a method of supporting a transition metal compound and a promoter compound for an olefin polymerization catalyst on a carrier, a physical adsorption method or a chemical adsorption method may be used.

In an exemplary embodiment, the physical adsorption method includes a method in which a solution in which a transition metal compound for an olefin polymerization catalyst is dissolved is contacted with a carrier and then dried; a method in which a solution in which a transition metal compound for olefin polymerization catalyst and a co- Or a method in which a solution in which a transition metal compound for an olefin polymerization catalyst is dissolved is contacted with a carrier and dried to prepare a carrier carrying thereon a transition metal compound for an olefin polymerization catalyst, To contact the carrier and drying the carrier to prepare a carrier carrying the promoter compound and then mixing them.

In an exemplary embodiment, the chemical adsorption method is a method in which a promoter compound is first supported on the surface of a support, and then a transition metal compound for an olefin polymerization catalyst is supported on the promoter compound, or a method in which a functional group (e.g., A method of covalently bonding a catalyst compound with a hydroxyl group (-OH) on the silica surface in the case of silica).

Hereinafter, specific examples of the olefin-based polymer of the present invention and specific examples for measuring physical properties of the produced olefin-based polymer will be described.

The transition metal compounds represented by A-2 and A-3 are synthesized by Ewen and Razavi in J. Am. Chem. Soc. Chem. Soc., 110, 6255 (1988) and J. Organomet. Chem., 435, 299 (1992). The transition metal compound represented by A-2 was prepared by a method known in the above-mentioned literature, and the transition metal compound represented by A-3 was prepared by the method of Example 1 below.

[Example 1] Preparation of Me ₂ C (Cp) (2,7- tert -Bu-Flu) HfMe ₂ (Transition metal compound represented by A-3)

Step A: Preparation of the ligand 2,2 - [(cyclopentadienyl) - (2,7-di- tert -butylfluorenyl)] propane

To a solution of 2,7-di- tert- butylfluorene (1 g, 3.59 mmol) in diethyl ether (15 mL) was added MeLi (1.73 g, 3.77 mmol, 1.6 M in diethyl ether) at -30 ^° C The temperature was raised to room temperature and the mixture was stirred for 3 hours. 6,6-dimethylfulvene (400 mg, 3.77 mmol) was diluted in diethyl ether (5 mL), added at -30 ^° C, and then the temperature was raised to room temperature and stirred for 12 hours.

After completion of the reaction, the mixture was extracted with diethyl ether and aqueous NH ₄ Cl. The organic layer was separated and purified by column chromatography (hexane: dichloromethane = 100: 1, v / v) to obtain the ligand 2,2 - [(cyclopentadienyl) - -di- tert- butylfluorenyl)] propane (1.04 g, 75%).

Step B: [(cyclopentadienyl) - (2,7-di- tert -butylfluorenyl)] dilithium Synthesis of compounds

2,2 - [(cyclopentadienyl) - (2,7-di- tert- butylfluorenyl)] propane N- BuLi (689 mg, 1.62 mmol, 1.6 M in hexane) was added at -30 ^° C to a solution of sodium hydride (304 mg, 0.79 mmol) in diethyl ether (10 mL) Lt; / RTI &gt; The resulting solid was filtered and dried under vacuum to give [(cyclopentadienyl) - (2,7-di- tert- butylfluorenyl)] dilithium 316 mg (100%) of the compound is obtained.

Step C: Isopropylidene [(cyclopentadienyl) - (2,7-di- tert -butylfluorenyl)] hafnium dichloride

To a solution of HfCl ₄ (94 mg, 0.29 mmol) in toluene (5 mL) was added isopropylidene [(cyclopentadienyl) - (2,7-di- tert -butylfluorenyl)] dilithium (116 mg, 0.29 mmol) in toluene (5 mL) was added at -30 ^° C, the temperature was raised to room temperature and stirred for 48 hours. After completion of the reaction, the reaction mixture was extracted with toluene, filtered, and then toluene was removed under vacuum. The residue was washed with hexane to obtain Isopropylidene [(cyclopentadienyl) - (2,7-di- tert -butylfluorenyl)] hafnium dichloride 105 mg (57%) of the compound is obtained.

Step D: Me ₂ C (Cp) (2,7- tert -Bu-Flu) HfMe ₂ Synthesis of

Isopropylidene [(cyclopentadienyl) - (2,7-di- tert- butylfluorenyl)] hafnium dichloride A solution of MeMgBr (130 mg, 0.38 mmol, 3.0 M in diethyl ether) in toluene (2 mL) was added to a solution of sodium hydride (95 mg, 0.15 mmol) in toluene (8 mL) at -30 ^° C Stir for 2 hours while refluxing at 70 ^° C. After completion of the reaction, the reaction mixture was extracted with toluene, filtered, and toluene was removed under vacuum to obtain 87 mg (97) of Me ₂ C (CP) (2,7- tert- Bu-Flu) HfMe ₂ %).

_{^{[1 H-NMR (C 6}} D 6, 300 MHz): 7.93 (d, 2H), 7.69 (s, 2H), 7.44-7.38 (m, 2H), 6.05 (t, 2H), 5.45 (t, 2H ), 2.03 (s, 6H), 1.29 (s, 18H), 1.31 (s, 6H).

[Example 2] Production of ethylene / 1-octene copolymer

An ethylene / 1-octene copolymer was prepared using an autoclave continuous process reactor. Specifically, after the autoclave continuous process reactor was filled with 1-octene, a triisobutyl aluminum compound (0.682 mmol / min), a transition metal compound represented by A-2 or A-3 prepared above (0.08 μmol / min ) And dimethylanilinium tetrakis (pentafluorophenyl) borate promoter (0.45 μmol / min) were simultaneously introduced into the reactor. Ethylene (0.5 kg / h) was then fed into the autoclave reactor and maintained at 150 ° C for 10 minutes or more in a continuous process at a pressure of 90 bar, followed by copolymerization reaction to obtain Copolymers (Production Examples 1 to 5) . Production Examples 1 to 5 were obtained by varying the input amount of 1-octene and the hydrogen input amount in the above production method.

Table 1 summarizes the polymerization conditions of Production Examples 1 to 5 above.

Manufacturing example catalyst 1-octene charge
(ml / min) Hydrogen input amount
(g / hr) Catalytic activity
(KgPE / gCat · hr) One A-2 9.3 0.2 221 2 A-2 7.5 0.2 195 3 A-2 9.3 0.3 215 4 A-3 11.2 0.0 158 5 A-3 7.2 0.3 168

[Experimental Example] Measurement of physical properties of ethylene / 1-octene copolymer

The physical properties of the polymers prepared in Preparation Examples 1 to 5 were measured and are shown in Table 2 below. Conventional copolymers (Comparative Examples 1 and 2) were obtained for comparison and the properties were measured together. In Comparative Example 1 and Comparative Example 2, Affinity 1900 and Affinity 1950 from DOW were used, respectively.

The DSC curves for the above Production Examples 1 to 5 and Comparative Examples were obtained using a differential scanning calorimeter (DSC, DSC 2920), and the melting temperature (Tm) and the crystallinity were measured Respectively. The first crystallinity means the degree of crystallization at the first melting temperature Tm1 and the second degree of crystallinity means the degree of crystallization at the second melting temperature Tm2.

1 to 3 are DSC curves for the copolymers of Production Examples 1 to 3, respectively. The first crystallinity and the second crystallinity were obtained by using Figs. 1 to 3 and the following equation (3).

[Formula 3]

First crystallinity (%) =? H _{measurement 1} /? H _100% * 100,? H _100% = 290 (J / g)

Second crystallinity (%) =? H _{measurement 2} /? H _100% * 100,? H _100% = 290 (J / g)

Here, the? H _{measurement 1} means a melting heat corresponding to the area of the region including the first melting temperature and the? H _{measurement 2} means the melting heat corresponding to the area of the region including the second melting temperature.

The total crystallinity refers to the sum of the first crystallinity and the second crystallinity, and the crystallinity ratio represents the ratio of the first crystallinity to the second crystallinity.

The weight average molecular weight (Mw) and the molecular weight distribution (MWD) were measured by Gel Permeation Chromatography (GPC). The softening point was measured using the ring and ball softening method (ASTM D-36). Specifically, in order to measure the softening point, about 5 to 6 g of a sample is put in a ring for making a specimen, and the molten specimen is melted by heating. After the molten specimen is cooled, a ball is put on a cooled resin, The softening point was measured as the ball of the resin reached the softening point while the temperature was increased.

EX Comonomer (wt%) Density (g / cm3) Mw (g / mol) MWD Softening point (℃) Tm1 (占 폚) Tm2 (占 폚) The first crystallinity (%) Second crystallinity (%) Total crystallinity (%) The crystallinity ratio (first crystallinity: second crystallinity Production Example 1 30.4 0.865 27,302 1.86 101.3 56.3 103.6 8.11 0.37 8.48 96: 4 Production Example 2 26.9 0.876 31,211 1.70 104.1 70.5 107.1 11.66 0.42 12.08 97: 3 Production Example 3 31.4 0.865 19,942 2.40 92.9 52.0 103.7 9.15 0.42 9.57 96: 4 Production Example 4 33.8 0.865 45,791 2.14 97.2 52.8 98.5 4.54 0.12 5.66 80:20 Production Example 5 30.1 0.875 5,715 2.40 91.8 69.1 89.8 13.27 2.49 15.86 84:16 Comparative Example 1 33.7 0.870 23,535 1.65 83.6 69.5 10.26 Comparative Example 2 31.3 0.874 26,490 1.64 86.7 73.0 11.08

As shown in Table 2, the olefin-based polymer of the present invention had a first melting temperature (Tm1) and a second melting temperature (Tm2) although it was produced under a single catalyst.

In addition, the olefin polymer of the present invention has two melting points, has a total crystallinity and density similar to those of the comparative examples, and has a high softening point within the crystallinity and density range as compared with the comparative examples. Accordingly, the olefin-based polymer of the present invention is excellent in heat resistance and adhesiveness and exhibits excellent performance in a hot melt adhesive or the like.

Hereinafter, embodiments belonging to the spirit of the invention will be described with reference to the above-described chemical structures, production examples, and the like. However, the spirit of the invention is not limited to the exemplary chemical structures and the production examples, and the ideas of the invention can be variously modified based on the exemplified chemical structures and the manufacturing examples. It is to be understood that both the foregoing general description and the appended claims are intended to provide further understanding of the scope of the inventive concept to those skilled in the art and do not limit the scope of the inventive idea to the scope of the claims . It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (17)

An olefin-based polymer formed by copolymerization of an olefin-based monomer and an olefin-based comonomer,
A softening point of 80 to 120 캜,
A first melting temperature and a second melting temperature,
Wherein the first melting temperature and the second melting temperature have different values. The method according to claim 1,
Wherein the difference between the first melting temperature and the second melting temperature is from 10 캜 to 80 캜. The method according to claim 1,
Wherein the first melting temperature is from -20 DEG C to 80 DEG C,
And the second melting temperature is 80 占 폚 to 140 占 폚. The method of claim 3,
Wherein the total crystallinity is 2% to 20%. 5. The method of claim 4,
Wherein the total crystallinity is 5% to 15%. The method of claim 3,
Wherein the ratio of the first crystallinity, which is the crystallinity to the first melting temperature, and the second crystallinity, which is the crystallinity to the second melting temperature, is 99: 1 to 75:25. The method of claim 3,
The weight average molecular weight of the olefin polymer is from 5,000 g / mol to 60,000 g / mol. 8. The method of claim 7,
An olefin polymer having a molecular weight distribution of 1.3 to 3.0. The method according to claim 1,
Wherein the content of the comonomer is 10 wt% to 50 wt%. The method according to claim 1,
And a density of 0.860 g / cm 3 to 0.900 g / cm 3. The method according to claim 1,
Olefin-based polymer formed by copolymerization under an olefin polymerization catalyst comprising a transition metal compound represented by the following formula (A-1).
&Lt; Formula (A-1) >

(In the above formula (A-1)
M is titanium (Ti), zirconium (Zr) or hafnium (Hf)
X is independently selected from the group consisting of halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkyl, amido, C _6-20 aryl or C _1-20 amido an alkylidene,
Q ₂ is carbon (C), silicon (Si), germanium (Ge), or tin (Sn)
R ¹ to R ¹⁴ are each independently hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted Substituted or unsubstituted C _1-6 alkyl, C _1-20 alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl , Or substituted or unsubstituted C _1-20 silyl,
Two or more adjacent ones of R ¹ to R ¹² may be connected to each other to form a substituted or unsubstituted C _4-20 ring) 12. The method of claim 11,
Wherein M is zirconium or hafnium,
Each X is independently halogen or C _1-20 alkyl,
Q &lt; ₂ &gt; is carbon or silicon,
R ¹ to R ⁵ , R ⁷ to R ¹⁰ and R ¹² are each hydrogen,
Wherein R ⁶ and R ¹¹ are each independently hydrogen, substituted or unsubstituted C _1-20 alkyl, or substituted or unsubstituted C _6-20 aryl,
Wherein each of R ¹³ to R ¹⁴ is independently hydrogen, or substituted or unsubstituted C _1-20 alkyl. 13. The method of claim 12,
The olefin-based polymer represented by the above formula (A-1) is represented by the following formula (A-2).
&Lt; Formula (A-2) >

13. The method of claim 12,
The olefin-based polymer represented by the above formula (A-1) is represented by the following formula (A-3).
&Lt; Formula (A-3)

The method according to claim 1,
Wherein at least one of the olefin-based monomer and the olefin-based comonomer comprises an alpha-olefin. 16. The method of claim 15,
The olefin-based monomer and the olefin-based comonomer are ethylene and 1-octene-based olefin polymers, respectively. An adhesive comprising the olefinic polymer according to any one of claims 1 to 16.

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