KR101939777B1 - Polyolefin - Google Patents

Abstract

Provided is an olefin-based polymer. According to the present invention, the olefin polymer has a melt tension (MT) of 80 mN or more and a maximum processing speed (velocity at break) of 200 mm/s or more. According to the present invention, the olefin-based polymer has high melt index and molecular weight characteristics, and simultaneously satisfies excellent melt strength and high speed processability.

Description

[0001] POLYOLEFIN [0002]

The present invention relates to an olefin-based polymer, and more specifically to an olefin-based polymer having excellent melt tension and high-speed processability.

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

On the other hand, it is generally known that the melt tension and the high-speed processability of a polymer are in a trade-off relationship in which one is increased and the other is decreased. For example, when the polymer is synthesized / processed to have a large amount of LCB (Long Chain Branch), the melt tension is improved but the high-speed processability may deteriorate.

A problem to be solved by the present invention is to provide an olefin polymer having excellent melt tension and high processability simultaneously.

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.

In order to solve the above problems, the olefin polymer according to one embodiment of the present invention has a melt tension (MT) of 80 mN or more and a maximum processing speed (Velocity at break) of 200 mm / s or more.

The olefin-based polymer may have a melt index (MI) of 0.5 to 1.7 g / 10 min.

The olefin-based polymer may have an LCB (Long Chain Branch) ratio of 1 to 3.

The olefin-based polymer may satisfy the following formula (1).

[Formula 1]

In the formula 1, Mn, Mw and Mz are number-average molecular weight, weight-average molecular weight and Z-average molecular weight, respectively.

The olefin-based polymer may satisfy the following formula (2).

[Formula 2]

In the formula 2, Mw and Mz are the weight average molecular weight and the Z average molecular weight, respectively.

The melt tension may be 100 to 200 mN.

The maximum processing speed may be 350 to 450 mm / s.

The melt index may be 1.0 to 1.6 g / 10 min.

The LCB ratio may be 1.5 to 2.5.

The olefin-based polymer may be a copolymer of an olefin-based monomer and an olefin-based comonomer.

The olefin-based polymer may have a unit molecular weight distribution.
The olefin-based polymer may have a density of 0.91 to 0.93 g / cc.

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According to another aspect of the present invention, there is provided a film comprising the above-mentioned 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 olefin-based polymer of the present invention can simultaneously satisfy excellent melt tension and high-speed processability while having high melt index and molecular weight characteristics.

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.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and the manner of achieving them, will be apparent from and elucidated with reference to the embodiments described hereinafter in conjunction with 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.

As used herein, the term " C _AB "means" the number of carbon atoms is not less than A and not more than B ", and the terms "A to B""inthe" substituted "means" at least one hydrogen of the hydrocarbon compound or a hydrocarbon derivative 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 substituted with alkylidene "means, and" unsubstituted "means" hydrocarbon compounds or at least one hydrogen, halogen, C _1-20 alkyl hydrocarbon derivatives, 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 alkylamido, C _6-20 arylamido or C _1-20 alkylidene ".

The olefin polymer according to an embodiment of the present invention may have a melt tension (MT) of 80 mN or more and a maximum processing speed (Velocity at break) of 200 mm / s or more.

The maximum processing speed means the speed measured immediately before the polymer is cut at the time of processing the polymer at a high speed, and can be an index indicating the high-speed processability of the olefin-based polymer. Specifically, as the processing speed increases, the polymer chain is relaxed as it is stretched in a single axis. The larger the main chain of the polymer is, the longer the polymer chains are loosened at high speed, and the polymer chains may be intertwined longer. Therefore, the fact that the maximum processing speed is high may mean that the ratio of the polymer having a large main chain is high.

On the other hand, the olefin polymer of the present invention may have a melt index (MI) of 0.5 to 1.7 g / 10 min and include LCB (Long Chain Branch). The olefin polymer of the present invention has an LCB Number, shape, etc., the melt tension and the maximum machining speed can be simultaneously high even though the melt index is high as described above. The melt index may be a value measured according to ASTM D1238 (2.16 Kg, 190 DEG C).

LCB is a long carbon branch attached to the main chain of the olefinic polymer and may particularly refer to branches having about 8 or more carbon atoms. Usually, comonomers include 1-butene, 1-hexene, 1- Lt; RTI ID = 0.0 > alpha-olefins. ≪ / RTI >

The olefin polymer of the present invention may have an LCB ratio of 1 to 3, and may satisfy the following formula (1).

[Formula 1]

In the formula 1, Mn, Mw and Mz mean a number-average molecular weight, a weight-average molecular weight and a Z-average molecular weight, respectively.

The above equation 1 means that the ratio of high molecular weight among the whole polymer distribution is larger, thereby increasing the entanglement and elasticity, which may mean that LCB is concentrated on the high molecular weight polymer chain. That is, although the number of LCBs is not excessively large, the olefinic polymer of the present invention may have a high value at the same time as the melt tension and the maximum processing speed, as described above, due to the specificity of its existence form.

The LCB ratio may be substantially the same as the peak ratio calculated according to the following formulas 2 to 5.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

The higher the peak ratio in Equation 5, the more LCBs are present.

The melt strength, the maximum machining speed, and a length 30 mm, diameter 2 mm, shear rate 72 / s of the capillary (capillary) and / or the initial speed of 18 mm / s, the wheel acceleration 12 mm / s ² (wheel) ≪ / RTI >

Specifically, the melt index, melt tension, LCB ratio and maximum processing speed of the olefinic polymer of the present invention can be as follows.

(1) Melt index: 1.0 to 1.6 g / 10 min

(2) Melting tension: 100 to 200 mN

(3) LCB ratio: 1.5 to 2.5

(4) Maximum machining speed: 350 to 450 mm / s

In a more specific embodiment, the olefinic polymer of the present invention may have a density of 0.91 to 0.93 g / cc, and may satisfy the following formula (6).

[Formula 6]

In the formula 6, Mw and Mz mean a weight-average molecular weight and a Z-average molecular weight, respectively.

The olefin-based polymer 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, and 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 .

Preferably, the olefin-based polymer may be a copolymer in which ethylene and 1-hexene are copolymerized, but is not limited thereto.

The olefinic polymer of the present invention can be polymerized by polymerization reaction such as, for example, free radical, cationic, coordination, condensation, addition, and the like, It is not.

In an exemplary embodiment, the olefin-based polymer may be produced by gas phase polymerization, solution polymerization, slurry polymerization or the like. Examples of the solvent that can be used when the olefinic polymer is prepared by solution polymerization or slurry polymerization 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.

The olefinic polymer of the present invention may have a unimodal molecular weight distribution. That is, the olefin-based polymer of the present invention may have a relatively narrow molecular weight distribution by including a single polymer component. Such a polymer may be one in which only one peak is observed when the molecular weight is measured by gel permeation chromatography (GPC).

The olefin polymer of the present invention may be one obtained by polymerization under an olefin polymerization catalyst comprising a first transition metal compound represented by the following formula A-1 and a second transition metal compound represented by the following formula B-1.

≪ Formula (A-1) >

<Formula B-1>

In the above formulas A-1 and B-1, n is an integer of 0 to 5, m is an integer of 0 to 2, and 1 may be an integer of 0 to 8. Specifically, n is 1, and m and l may be 0, respectively.

M may be titanium (Ti), zirconium (Zr) or hafnium (Hf). Specifically, 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. Specifically, X may each be a halogen. More specifically, each X may be chlorine (Cl).

Q may be carbon (C), silicon (Si), germanium (Ge), or tin (Sn). Specifically, Q may be silicon.

R ¹ to R ⁸ are each independently a substituted or unsubstituted C _1-20 alkyl, a substituted or unsubstituted C _2-20 alkenyl, a substituted or unsubstituted C _6-20 aryl, a substituted or 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, substituted Or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl have. Further, each of R ¹ to R ⁶ may independently form an adjacent or adjacent group to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring.

Specifically, R ¹ , R ² , R ⁷ and R ⁸ may each independently be C _1-20 alkyl. More specifically, R ¹ and R ² may each be C _1-6 alkyl, and R ⁷ and R ⁸ may each be methyl.

In an exemplary embodiment, the first and second transition metal compounds may be compounds represented by the following formulas A-2 and B-2, respectively. However, examples of the olefin polymerization catalyst of the present invention are not limited to the following compounds.

&Lt; Formula (A-2) >

<Formula B-2>

The first transition metal compound and the second transition metal compound may be contained in a weight ratio of 0.4 to 2.5: 1. Specifically, the first transition metal compound and the second transition metal compound may be contained in a weight ratio of 7: 3 to 3: 7. When the content ratio of the first transition metal compound and the second transition metal compound is within the above range, the olefin-based polymer having excellent melt tension and high-speed processability can be produced as described above.

The olefin polymerization catalyst 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 may further include a carrier that supports a first transition metal compound, a second transition metal compound, and a 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 is capable of supporting the first and second transition metal compounds 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 is dissolved is contacted with a carrier and then dried, a method in which a solution in which a transition metal compound and a promoter compound are dissolved is contacted with a carrier, A solution in which the compound is dissolved is brought into contact with a carrier and then dried to prepare a carrier carrying the transition metal compound; separately from the solution in which the co-catalyst compound is dissolved, the carrier is contacted with the carrier, And then mixing them, or the like.

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

The total amount of the first and second transition metal compound to be supported may be 0.001 mmol to 1 mmol based on 1 g of the carrier and the amount of the co-catalyst compound to be supported may be 2 mmol to 15 mmol based on 1 g of the carrier.

The carrier may contain one or two or more kinds of carriers, and the first transition metal compound and the second transition metal compound may be both supported on one carrier, and the first transition metal compound and the second transition A metal compound may be supported on the support, and only one of the first transition metal compound and the second transition metal compound may be supported on the support.

In an exemplary embodiment, the olefin polymerization catalyst may be a hybrid supported catalyst in which a first transition metal compound, a second transition metal compound, and a cocatalyst compound are supported together on silica, which is a carrier of a single species. However, the embodiment of the present invention is not limited thereto.

The present invention provides a film produced using the olefinic polymer described above according to another embodiment. The film may have excellent haze, clarity, modulus and the like by being produced by including the olefin-based polymer of the present invention.

Specifically, the film of the present invention may have at least one of the following characteristics (1) to (5).

(1) Turbidity: 15% or less

(2) Sharpness: 90% or more

(3) Young's modulus: more than 15,000 (MD), more than 17,000 (TD)

(4) 1% Secant Modulus: 3,000 or more (MD, TD)

(5) 2% Secant Modulus: 2,500 or more (MD), 2,800 or more (TD)

In an exemplary embodiment, the haze of the film of the present invention is less than about 7%, the clarity is greater than about 95%, the Young's modulus (MD) is greater than about 15,900, the 1% Secant modulus (TD) The modulus (MD) may be at least about 2,500, but is not limited thereto.

Hereinafter, the hybrid supported catalyst as the olefin polymerization catalyst of the present invention and a specific production example of the olefin based polymer and a specific example of measuring the physical properties of the produced olefin based polymer will be described.

[Preparation Example 1] Preparation of hybrid supported catalyst

The transition metal compound of Formula A-2 purchased from sPCI was used without purification and the transition metal compound of Formula B-2 was prepared by the method disclosed in U.S. Patent No. 5,883,275.

1.99 g of the compound of the formula A-2 and 2.25 g of the compound of the formula B-2 were mixed with 838 g of MAO (Al / Zr = 150) in a glove box and stirred for 2 hours at 2 L of RBF. 212 g of XPO-2402 silica and 500 mL of toluene were mixed in 3 L (RBF), and the solution was poured into a silica slurry and stirred in an oil bath at 75 캜 for 3 hours. The supported catalyst was washed three times with 500 mL of toluene and dried at 60 캜 under vacuum for 30 minutes to obtain 283 g of a mixed supported catalyst in the form of free-flowing powder (Production Example 1-1).

Further, a hybrid supported catalyst (Production Example 1-2) was obtained in the same manner as described above, except that 2.78 g and 1.35 g of the compound of the above formulas A-2 and B-2 were used, respectively.

[Preparation Example 2] Preparation of ethylene / 1-hexene copolymer

An ethylene / 1-hexene copolymer was prepared using a gas phase fluidized bed pilot reactor. Specifically, the catalyst prepared in the above Preparation Example was continuously fed into a gas phase fluidized bed pilot reactor, and the temperature and the partial pressure of ethylene were maintained at 80 ° C. and 14 kgf / cm ² , respectively, and MI and Density were measured. To obtain about 10 kg / hr of ethylene / 1-hexene copolymer continuously.

Table 1 summarizes the respective polymerization conditions using the hybrid supported catalyst of Production Example 1 above.

Example catalyst 1-hexene charge
(ml) Hydrogen input amount
(cc / min) Catalytic activity
(gPE / gCat · hr) One 1-1 50 One 4340 2 1-2 50 One 4800

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

The properties of the ethylene / 1-hexene copolymer (Examples 1 and 2) synthesized in Preparation Example 2 were measured and shown in Table 2 below. For comparison, conventional ethylene / 1-hexene copolymers (Comparative Examples 1 to 3) were obtained and their physical properties were measured.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 MI
(g / 10 min) 1.3 1.5 1.11 1.1 1.0 MFR 20.4 20.6 16.14 30.2 23.2 density
(g / cc) 0.923 0.923 0.920 0.918 0.920 Mn
(g / mol) 30,890 43,000 41,000 26230 48,620 Mw
(g / mol) 119,080 114,590 109,400 90,380 127,220 Mz
(g / mol) 489,040 354,840 227,150 195,270 288,910 PDI
(Mw / Mn) 3.85 2.66 2.61 3.45 2.2 Mz / Mw 4.11 3.10 2.07 2.16 2.27 η ₀ 16,300 14,600 7,100 60,800 33,200 MT
(mN) 166 164 70 101 114 Maximum machining speed
(mm / s) 380 396 367 398 208 LCB ratio 1.83 1.70 0.85 3.6 20.2

As shown in Table 2, the olefin polymer synthesized under the olefin polymerization catalyst of the present invention has a relatively high melt index (MI), a molecular weight characteristic (Mz / Mw) and the like, (MT) and the maximum machining speed at the same time.

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 (13)

10 min to 1.5 g / 10 min, a melt tension (MT) of 160 mN to 170 mN and a melt index (Melt Index) measured by ASTM D1238 (2.16 kg, 190 DEG C) A processing speed (Velocity at break) of 350 mm / s to 400 mm / s,
A long chain branch (LCB) ratio of 1.5 to 2.0,
An olefin-based polymer satisfying the following formula 1 and formula 2 and having a molecular weight distribution of unimodal.
[Formula 1]

[Formula 2]

Mn, Mw and Mz are number-average molecular weight, weight-avrage molecular weight and Z-average molecular weight, respectively, in the formulas 1 and 2, delete delete delete delete delete delete delete delete The method according to claim 1,
An olefin-based polymer which is a copolymer of an olefin-based monomer and an olefin-based comonomer. delete The method according to claim 1,
The olefin-based polymer has a density of 0.91 to 0.93 g / cc. A film comprising the olefinic polymer of any one of claims 1, 10 and 12.