KR20220135280A - Polypropylene based composite - Google Patents

Abstract

The present invention relates to a polypropylene based composite comprising: (A) polypropylene; and (B) an olefin polymer satisfying requirements of (1) melt index (MI, 190 ℃, 2.16 kg load conditions): 0.1 to 10.0 g/10 minutes, (2) density (d): 0.875 g/cc to 0.895 g/cc, (3) 0.5 J/g <= dH(100) <= 3.0 J/g and 1.0 J/g <= dH(90) <= 6.0 J/g when measuring a successive self-nucleation/annealing (SSA) measuring method, (4) 15 <= T(90)-T(50) <= 30 and 50 ℃ <= T(50) <= 75 ℃ when measuring the SSA measuring method, and (5) melting point (Tm) of 55 ℃ <= Tm <= 80 ℃ measured by a differential scanning calorimeter (DSC). The polypropylene based composite of the present invention has excellent flexural strength and impact strength.

Description

Polypropylene-based composite material {POLYPROPYLENE BASED COMPOSITE}

The present invention relates to a polypropylene-based composite, and more specifically, to a polypropylene-based composite having improved mechanical properties such as flexural strength without lowering impact strength, including a low-density olefin-based polymer having a high crystallinity region and exhibiting excellent mechanical rigidity. It's about composites.

In general, as a composition for automobile interior and exterior parts, a polypropylene-based resin composition containing polypropylene (PP) as a main component and an impact reinforcing material and an inorganic filler has been used.

Until the mid-1990s, before the development of ethylene-α-olefin copolymers polymerized by applying a metallocene catalyst, most polypropylene-based resin compositions were either EPR (Ethylene Propylene Rubber) or EPDM as materials for automobile interior and exterior materials, especially bumper covers. (ethylene propylene diene rubber) was mainly used as an impact reinforcing material. However, after the appearance of the ethylene-α-olefin copolymer synthesized by the metallocene catalyst, the ethylene-α-olefin copolymer has been used as an impact modifier and is now the mainstream. This is because the polypropylene-based composite material using this material has many advantages such as good formability and low price with balanced physical properties such as impact strength, elastic modulus, and flexural strength.

Polyolefins such as ethylene-α-olefin copolymer synthesized by a metallocene catalyst have a narrow molecular weight distribution and good mechanical properties because their molecular structure is more uniformly controlled than that of a Ziegler-Natta catalyst. Even in the low-density ethylene elastomer polymerized by the metallocene catalyst, since the α-olefin copolymer monomer is relatively uniformly inserted into the polyethylene (PE) molecule than that by the Ziegler-Natta catalyst, it is possible to maintain low-density rubber properties while maintaining other mechanical properties. It also has good physical properties.

However, there is a limit in securing impact resistance according to various usage environments, and the development of a polypropylene-based composite that can overcome this limitation is required.

US Patent No. 5,064,802 US Patent No. 6,548,686 KR 2007-0003071 A

The problem to be solved by the present invention is to provide a polypropylene-based composite material capable of exhibiting excellent mechanical strength properties such as significantly improved flexural strength without reduction in impact strength.

In order to solve the above problems, the present invention provides a polypropylene-based composite including (A) polypropylene, and (B) an olefin-based polymer satisfying the requirements of (1) to (5) below.

(1) Melt index (MI, 190 °C, 2.16 kg load condition): 0.1 to 10.0 g/10 min; (2) density (d): 0.875 to 0.895 g/cc; (3) 0.5 J/g≤dH(100)≤3.0 J/g, and 1.0 J/g≤dH(90)≤6.0 J/g when measured by differential scanning calorimetry (SSA); (4) 15≤T(90)-T(50)≤30 when measuring differential scanning calorimetry (SSA), and 50°C≤T(50)≤75°C; (5) measured by differential scanning calorimetry (DSC) As long as the melting temperature (Tm) is 55℃≤Tm≤80℃

Here, T(50) and T(90) are the temperatures at which 50% and 90% of each is melted when the temperature-heat capacity curve is fractionated from the differential scanning calorimetry precision measurement (SSA) measurement result, respectively, and dH(90) is It is the enthalpy of melting at 90°C or higher, and dH(100) represents the melting enthalpy at 100°C or higher.

The polypropylene-based composite according to the present invention includes an olefin-based polymer that exhibits excellent mechanical rigidity by introducing a high crystallinity region and can be uniformly dispersed in the composite with excellent miscibility with polypropylene, so that no additional additives are used. It can exhibit significantly improved mechanical strength properties along with excellent impact strength without

1 is a graph showing the results measured by differential scanning calorimetry precision measurement (SSA) for the polymers of Preparation Example 2 and Comparative Preparation Example 2;

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

The terms or words used in the present specification and claims are not to be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

As used herein, the term “polymer” refers to a polymer compound prepared by polymerization of monomers of the same or different types. The generic term "polymer" includes the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer". Also, the term “interpolymer” refers to a polymer prepared by polymerization of two or more different types of monomers. The generic term "interpolymer" refers to the term "copolymer" (which is commonly used to refer to polymers prepared from two different monomers) as well as the term "copolymer" (which is commonly used to refer to polymers prepared from three different types of monomers). used) the term "terpolymer". It includes polymers prepared by polymerization of four or more types of monomers.

In general, polypropylene is used as an interior and exterior material for automobiles such as automobile bumpers, and polyolefin-based polymers are also used as an impact reinforcing material to supplement the low impact strength of polypropylene. Among them, low-density polyolefin-based polymers are used to have high impact strength characteristics while exhibiting characteristics such as impact resistance, elastic modulus, and tensile properties according to various usage environments, but in this case, the problem of lowering the strength of polypropylene is rather there was.

In contrast, in the present invention, when the polypropylene-based composite is manufactured, an olefin-based polymer that exhibits an excellent impact strength improvement effect and can be uniformly dispersed in the composite with excellent miscibility with polypropylene is used, thereby providing excellent performance without using a separate additive. It can exhibit significantly improved impact strength properties along with mechanical strength.

The polypropylene-based composite material according to the present invention includes (A) polypropylene and (B) an olefin-based polymer satisfying the requirements of (1) to (5) below.

(1) Melt index (MI, 190 °C, 2.16 kg load condition): 0.1 to 10.0 g/10 min; (2) density (d): 0.875 to 0.895 g/cc; (3) 0.5 J/g≤dH(100)≤3.0 J/g, and 1.0 J/g≤dH(90)≤6.0 J/g when measured by differential scanning calorimetry precision measurement (SSA); (4) 15≤T(90)-T(50)≤30 in differential scanning calorimetry precision measurement (SSA), and 50°C≤T(50)≤75°C; (5) Melting temperature (Tm) measured by differential scanning calorimeter (DSC) is 55℃≤Tm≤80℃

Here, T(50) and T(90) are the temperatures at which 50% and 90% of each is melted when the temperature-heat capacity curve is fractionated from the differential scanning calorimetry precision measurement (SSA) measurement result, respectively, and dH(90) is It is the enthalpy of melting at 90°C or higher, and dH(100) represents the melting enthalpy at 100°C or higher.

Hereinafter, each component will be described in detail.

(A) polypropylene

In the polypropylene-based composite material according to an embodiment of the present invention, the polypropylene may be specifically a polypropylene homopolymer, or a copolymer of propylene and an alpha-olefin monomer, wherein the copolymer is alternately ( alternating) or random, or block copolymers. However, in the present invention, the polypropylene that may overlap with the olefin polymer is excluded, and is a compound different from the olefin polymer.

The alpha-olefin-based monomer may be specifically an aliphatic olefin having 2 to 12 carbon atoms, or 2 to 8 carbon atoms. More specifically, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1- Octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aitocene, 4,4-dimethyl-1-pentene, 4,4- and diethyl-1-hexene or 3,4-dimethyl-1-hexene, and any one or a mixture of two or more thereof may be used.

More specifically, the polypropylene may be any one or a mixture of two or more selected from the group consisting of a polypropylene copolymer, a propylene-alpha-olefin copolymer, and a propylene-ethylene-alpha-olefin copolymer. Copolymers may be random or block copolymers.

In addition, the polypropylene has a melt index (MI) of 0.5 g/10min to 100 g/10min measured at 230°C and a load of 2.16 kg, specifically, the melt index (MI) is 1 g/10min to 90 g/min. It can be 10 min. If the melt index of polypropylene is out of the above range, there is a possibility that a problem may occur during injection molding.

Specifically, in the polypropylene-based composite material according to an embodiment of the present invention, the polypropylene has a melt index (MI) of 0.5 g/10min to 100 g/10min, specifically measured at 230° C. and a load of 2.16 kg. It may be an impact copolymer of 1 g/10min to 90 g/10min, and more specifically, it may be a propylene-ethylene impact copolymer, and the impact copolymer is 20 weight based on the total weight of the polypropylene-based composite material. % to 90 wt%, specifically 30 wt% to 70 wt%, more specifically 40 wt% to 60 wt% may be included. When the impact copolymer having such physical properties is included in the above-described content range as polypropylene, strength characteristics, particularly, strength characteristics at room temperature can be improved.

The above-described impact copolymer may be prepared to satisfy the above-described physical property requirements using a conventional polymer manufacturing reaction, or may be commercially obtained and used. Specific examples include SEETEC™ M1600 manufactured by LG Chem.

In addition, in the polypropylene-based composite material according to an embodiment of the present invention, the polypropylene has a DSC melting point in the range of 120° C. to 160° C., and 230° C. according to ASTM-D 1238, measured under load conditions of 2.16 kg , at least one random propylene copolymer having a melt flow rate (MFR) in the range of 5 g/10 min to 120 g/10 min, wherein the random propylene copolymer is 20 wt% to 90 wt% based on the total weight of the polypropylene-based composite material , specifically 30 wt% to 70 wt%, more specifically 40 wt% to 60 wt% may be included. When polypropylene having such physical properties is included in the above-described content range, mechanical strength of the polypropylene composite material such as hardness may be improved. The random propylene copolymer may be prepared to satisfy the above-described physical property requirements using a conventional polymer preparation reaction, or may be commercially obtained and used. Specific examples include Braskem™ PP R7021-50RNA from Braskem America Inc. or Formolene™ 7320A from Formosa Plastics Corporation.

(B) Olefin polymer

The olefin-based polymer included in the polypropylene-based composite according to the present invention has a low density, and a high crystallinity region is introduced compared to a conventional olefin-based polymer, so that the same level of density and melt index (Melt Index, MI, 190°C, 2.16 kg load condition), it shows higher tensile strength, flexural modulus and hardness. The olefin-based polymer included in the polypropylene-based composite according to the present invention is prepared by a manufacturing method comprising the step of polymerizing an olefin-based monomer by introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization, hydrogen during polymerization A highly crystalline region may be introduced according to the gas input, thereby exhibiting excellent mechanical rigidity.

The melt index (MI) can be adjusted by controlling the amount of the catalyst used in the process of polymerizing the olefin-based polymer for the comonomer, and affects the mechanical properties and impact strength, and moldability of the olefin-based polymer. In the present specification, the melt index is measured under a low density condition of 0.875 g / cc to 0.895 g / cc according to ASTM D1238 at 190 ° C. and a load of 2.16 kg, and the olefin-based polymer is (1) melt index (MI ) satisfies the requirement of 0.1 g/10 min to 10.0 g/10 min, and the melt index (MI) is specifically 0.3 g/10 min or more, 0.4 g/10 min or more, 9.0 g/10 min or less, 7.0 g /10 minutes or less.

On the other hand, the olefin-based polymer (2) satisfies the requirement that the density (d) is 0.875 g/cc to 0.895 g/cc, and the density (d) is specifically 0.876 g/cc or more, 0.878 g/cc or more, 0.892 g/cc or less and 0.891 g/cc or less.

In general, the density of the olefin-based polymer is affected by the type and content of the monomer used during polymerization, the degree of polymerization, and the like, and in the case of the copolymer, the content of the comonomer is greatly affected. The olefin-based polymer included in the polypropylene-based composite of the present invention is polymerized using a catalyst composition including a transition metal compound having a characteristic structure, and a large amount of comonomer can be introduced, resulting in a low density in the above-described range. can have

In addition, the olefin-based polymer is (3) 0.5 J/g≤dH(100)≤3.0 J/g when measured by differential scanning calorimetry (SSA), and 1.0 J/g≤dH(90)≤6.0 J/g The phosphorus requirement is satisfied, and specifically, the dH (100) may be 0.9 J/g or more, 0.95 J/g or more, 2.0 J/g or less, 1.9 J/g or less, and the dH (90) is 1.5 J/g or more, 1.6 J/g or more, 5.0 J/g or less, and 4.5 J/g or less.

In addition, the olefin-based polymer satisfies the requirements of (4) 15≤T(90)-T(50)≤30 and 50℃≤T(50)≤75℃ when measured by differential scanning calorimetry (SSA), , specifically, the T(90)-T(50) may be 16 or more, 17 or more, and 25 or less, and the T(50) may satisfy the requirements of 52 ℃ or more, 54 ℃ or more, 74 ℃ or less, 73 ℃ or less. have.

In addition, the olefin-based polymer satisfies (5) the requirement that the melting temperature (Tm) measured by differential scanning calorimetry (DSC) is 55°C≤Tm≤80°C, specifically, the melting temperature (Tm) is 60°C or higher, It may be 65°C or higher, 80°C or lower, or 75°C or lower.

In addition, the olefin-based polymer may additionally satisfy the requirement that (6) a glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) is -70°C≤Tg≤-43°C, and specifically, the glass transition temperature ( Tg) may be -60°C or higher, -51°C or higher, and -43°C or lower.

The melting temperature can be obtained using a differential scanning calorimeter (DSC), and after heating at a constant rate to a temperature approximately 30°C higher than the melting temperature (Tm), and then to a temperature approximately 30°C lower than the glass transition temperature (Tg) After the first cycle of cooling at a constant rate, the peak of the standard melting temperature (Tm) can be obtained in the second cycle. For example, using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 250), the temperature is increased to 150°C, held at that temperature for 1 minute, then lowered to -100°C, and the DSC curve is obtained by increasing the temperature again Observe and measure the peak of the DSC curve as the melting point (melting temperature).

In addition, the olefin-based polymer according to an example of the present invention may further satisfy the requirement of (7) a weight average molecular weight (Mw) of 10,000 g/mol to 500,000 g/mol, and specifically, the weight average molecular weight (Mw) is It may be 30,000 g/mol or more, 50,000 g/mol or more, 300,000 g/mol or less, and more specifically 200,000 g/mol or less. In the present invention, the weight average molecular weight (Mw) is a polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC).

In addition, the olefin-based polymer according to an example of the present invention additionally has a ratio (Mw/Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) (8) Molecular Weight Distribution (MWD) of 0.1 to 6.0 The phosphorus requirement may be satisfied, and the molecular weight distribution (MWD) may be specifically 1.0 or more, 2.0 or more, 4.0 or less, and 3.0 or less.

In addition, the olefin-based polymer may additionally satisfy the requirement of (9) a melt flow rate ratio (MFRR) of 5 to 10, which is a ratio (Mw/Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn). Specifically, the melt flow rate ratio may be 6 or more, 9 or less, or 8 or less.

The melt flow rate ratio (MFRR) means the ratio obtained by dividing MI ₁₀ (melt index under a load of 10 kg and 190 ° C.) by MI _2.16 (melt index under a load of 2.16 kg and 190 ° C.) of the long side chain (LCB) of the polymer. As the number decreases, the MFRR may exhibit a low value, and mechanical properties of the polymer may be improved.

The olefin-based polymer may have an elution temperature (Te) of 30° C. to 40° C. when measured by cross-fractionation chromatography (CFC), and the elution temperature (Te) is specifically 31° C. or more, 32° C. or more. , 40 ℃ or less, 39 ℃ or less. The elution temperature (Te) is the temperature of the highest point of the peak that exists after -20°C in the temperature-elution amount graph when measuring cross-fraction chromatography (CFC) for the olefin-based polymer, and the polypropylene-based composite of the present invention is included The olefin-based polymer to be used may have one peak after -20°C, that is, it may have one elution temperature (Te).

The (B) olefin-based polymer is an olefin-based monomer, specifically, an alpha-olefin-based monomer, a cyclic olefin-based monomer, a diene olefin-based monomer, a triene olefin-based monomer, and a styrene-based monomer. Or it may be a copolymer of two or more types. More specifically, the olefin-based polymer may be a copolymer of ethylene and an alpha-olefin having 3 to 12 carbon atoms or a copolymer of ethylene and an alpha-olefin having 3 to 10 carbon atoms.

The alpha-olefin comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene , 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1,5 - It may include any one or a mixture of two or more selected from the group consisting of -pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

More specifically, the olefin-based polymer included in the polypropylene-based composite according to an example of the present invention is ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4-methyl-1-pentene, or ethylene and 1 It may be a copolymer of -octene, and more specifically, the olefin copolymer according to an example of the present invention may be a copolymer of ethylene and 1-butene.

When the olefin-based polymer is a copolymer of ethylene and alpha-olefin, the amount of the alpha-olefin is 90 wt% or less, more specifically 70 wt% or less, even more specifically 5 wt% to 60 wt% based on the total weight of the copolymer. It may be weight %, and more specifically, it may be 20 weight % to 50 weight %. When the alpha-olefin is included in the above range, the above-described physical properties may be appropriately implemented.

The olefin-based polymer having the above physical properties and structural characteristics is a continuous solution polymerization reaction in which hydrogen gas is introduced in a single reactor in the presence of a metallocene catalyst composition including one or more transition metal compounds to polymerize the olefin-based monomer. can be manufactured through Accordingly, in the olefin-based polymer included in the polypropylene-based composite of the present invention, a block is not formed in which two or more repeating units derived from any one of the monomers constituting the polymer in the polymer are linearly connected. That is, the olefin-based polymer included in the polypropylene-based composite according to the present invention does not include a block copolymer, and a random copolymer, an alternating copolymer, and a graft copolymer. copolymer) may be selected from the group consisting of, and more specifically, may be a random copolymer.

In an example of the present invention, the amount of the hydrogen gas input may be 0.35 to 3.00 parts by weight, specifically 0.4 to 2.0 parts by weight, more specifically 0.45 to 1.50 parts by weight, based on 1 part by weight of the olefinic monomer added to the reaction system. can be negative In addition, in an example of the present invention, when the olefin-based polymer is polymerized by continuous solution polymerization, the hydrogen gas is 0.35 to 3.0 kg/h, specifically 0.4 to 1 kg/h of the olefinic monomer introduced into the reaction system. to 2.0 kg/h, more specifically 0.45 to 1.50 kg/h.

In addition, in another example of the present invention, when the olefin-based polymer is a copolymer of ethylene and alpha-olefin, the hydrogen gas is 0.8 to 3.0 parts by weight, specifically 0.90 to 2.8 parts by weight, based on 1 part by weight of ethylene, More specifically, it may be added in an amount of 1.0 to 2.7 parts by weight. In addition, in one example of the present invention, when the olefin-based polymer is a copolymer of ethylene and alpha-olefin, and is polymerized by continuous solution polymerization, the hydrogen gas is 0.8 to 1 kg/h of ethylene introduced into the reaction system. 3.0 kg/h, specifically 0.90 to 2.8 kg/h, more specifically 1.0 to 2.7 kg/h.

When polymerization is performed under the conditions in which the hydrogen gas is introduced in an amount within the above range, the olefin-based polymer included in the polypropylene-based composite of the present invention may satisfy the above-described physical properties.

Specifically, the olefin-based copolymer included in the polypropylene-based composite of the present invention comprises a step of polymerizing the olefin-based monomer by introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of Formula 1 below It can be obtained by a manufacturing method comprising

However, in the preparation of the olefin-based polymer according to an embodiment of the present invention, the scope of the structure of the transition metal compound of Formula 1 is not limited to the specific disclosed form, and all changes included in the spirit and technical scope of the present invention; It should be understood to include equivalents and substitutes.

[Formula 1]

In Formula 1,

R ₁ is the same as or different from each other, and each independently represents hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, silyl, alkylaryl having 7 to 20 carbon atoms, and 7 to 20 carbon atoms. of arylalkyl or a metalloid radical of a Group 4 metal substituted with hydrocarbyl, wherein the two R ₁ are linked to each other by an alkylidine radical containing an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms. to form a ring;

R ₂ are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryloxy having 6 to 20 carbon atoms; or an amido radical, wherein two or more of R ₂ may be connected to each other to form an aliphatic ring or an aromatic ring;

R ₃ are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; or an aliphatic or aromatic ring containing nitrogen, substituted or unsubstituted with an aryl radical, and when the substituents are plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;

M is a Group 4 transition metal;

Q ₁ and Q ₂ are each independently halogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkyl amido having 1 to 20 carbon atoms; aryl amido having 6 to 20 carbon atoms; or an alkylidene radical having 1 to 20 carbon atoms.

In addition, in another example of the present invention, in Formula 1, R ₁ and R ₂ Are the same as or different from each other, and each independently hydrogen; alkyl having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or silyl,

R ₃ are the same as or different from each other, and alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl; alkoxy having 1 to 20 carbon atoms; aryloxy having 6 to 20 carbon atoms; or amido; At least _{two of R 3 may} be connected to each other to form an aliphatic or aromatic ring;

The Q ₁ and Q ₂ are the same as or different from each other, and each independently halogen; alkyl having 1 to 20 carbon atoms; alkylamido having 1 to 20 carbon atoms; It may be an arylamido having 6 to 20 carbon atoms,

M may be a Group 4 transition metal.

Further, in another example of the present invention, in Formula 1, R ₁ And R ₂ Are the same as or different from each other, and each independently hydrogen; alkyl having 1 to 12 carbon atoms; Or it may be an aryl having 6 to 12 carbon atoms,

R ₃ are the same as or different from each other, and alkyl having 1 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; or aryl having 6 to 12 carbon atoms;

The Q ₁ and Q ₂ are the same as or different from each other, and each independently halogen; Or it may be an alkyl having 1 to 12 carbon atoms,

M may be Ti.

The transition metal compound represented by Chemical Formula 1 has a metal site connected by a cyclopentadienyl ligand into which tetrahydroquinoline is introduced, and thus the Cp-MN angle is structurally narrow, and the Q ₁ -MQ ₂ angle that the monomer approaches is wide. features to retain. In addition, Cp, tetrahydroquinoline, nitrogen and metal sites are sequentially linked by a ring bond to form a more stable and rigid pentagonal ring structure. Therefore, when these compounds are activated by reacting them with a cocatalyst such as methylaluminoxane or B(C ₆ F ₅ ) ₃ and then applied to olefin polymerization, olefinic compounds having high activity and high copolymerizability even at high polymerization temperatures It is possible to polymerize the polymer.

Each of the substituents defined in the present specification will be described in detail as follows.

As used herein, the term 'hydrocarbyl group' is, unless otherwise stated, the number of carbon atoms consisting only of carbon and hydrogen, regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl or arylalkyl. It means a monovalent hydrocarbon group of 1 to 20.

As used herein, the term 'halogen' means fluorine, chlorine, bromine or iodine, unless otherwise noted.

The term 'alkyl' as used herein, unless otherwise stated, refers to a straight-chain or branched hydrocarbon residue.

As used herein, the term 'cycloalkyl' refers to cyclic alkyl including cyclopropyl and the like, unless otherwise specified.

As used herein, the term 'alkenyl' refers to a straight-chain or branched alkenyl group, unless otherwise specified.

The branched chain is alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.

The term 'aryl' as used herein refers to an aromatic group having 6 to 20 carbon atoms, unless otherwise specified, specifically phenyl, naphthyl, anthryl, phenanthryl, chrysenyl, pyrenyl, anthracenyl, pyridyl, dimethyl anilinyl, anisolyl, and the like, but are not limited thereto.

The alkylaryl group means an aryl group substituted by the alkyl group.

The arylalkyl group means an alkyl group substituted by the aryl group.

The ring (or heterocyclic group) means a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 ring atoms and containing at least one hetero atom, and may be a single ring or a condensed ring of two or more rings. In addition, the heterocyclic group may be unsubstituted or substituted with an alkyl group. Examples thereof include indoline and tetrahydroquinoline, but the present invention is not limited thereto.

The alkyl amino group means an amino group substituted by the alkyl group, and includes, but is not limited to, a dimethylamino group, a diethylamino group, and the like.

According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is limited to these examples only. not.

In the present specification, silyl may be silyl substituted or unsubstituted with alkyl having 1 to 20 carbon atoms, for example, silyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl , triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris(trimethylsilyl)silyl, and the like, but are not limited thereto.

The compound of Formula 1 may be of Formula 1-1, but is not limited thereto.

[Formula 1-1]

In addition, it may be a compound having various structures within the range defined in Formula 1 above.

Since the transition metal compound of Formula 1 can introduce a large amount of alpha-olefin as well as low-density polyethylene due to the structural characteristics of the catalyst, it is possible to prepare a low-density polyolefin copolymer of 0.875 g/cc to 0.895 g/cc. .

The transition metal compound of Formula 1 may be prepared by the following method as an example.

[Scheme 1]

In Scheme 1, R ₁ to R ₃ , M, Q ₁ and Q ₂ are as defined in Formula 1 above.

Formula 1 may be prepared according to the method described in Korean Patent Publication No. 2007-0003071, and the entire contents of the patent document are included in the present specification.

The transition metal compound of Formula 1 may be used as a catalyst for a polymerization reaction in the form of a composition further comprising at least one of the cocatalyst compounds represented by Formula 2, Formula 3, and Formula 4 in addition to the above.

[Formula 2]

-[Al(R ₄ )-O] _a -

[Formula 3]

A(R ₄ ) ₃

[Formula 4]

[LH] ⁺ [W(D) ₄ ] ^- or [L] ⁺ [W(D) ₄ ] ^-

In Formulas 2 to 3,

R ₄ may be the same as or different from each other, and are each independently selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,

A is aluminum or boron,

D is each independently aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, wherein the substituent is halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms and at least one selected from the group consisting of aryloxy having 6 to 20 carbon atoms,

H is a hydrogen atom,

L is a neutral or cationic Lewis base,

W is a group 13 element,

a is an integer greater than or equal to 2;

Examples of the compound represented by Formula 2 include alkylaluminoxanes such as methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and two or more of the alkylaluminoxanes are mixed and modified alkylaluminoxane, and specifically may be methylaluminoxane and modified methylaluminoxane (MMAO).

Examples of the compound represented by Formula 3 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and specifically may be selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.

Examples of the compound represented by Formula 4 include triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, trimethylammoniumtetra (o,p-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetrapentafluorophenylboron, N,N -diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtetraphenylboron, dimethyl Anilinium tetrakis(pentafluorophenyl)borate, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra(p-tolyl)aluminum, tri Propylammoniumtetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammoniumtetra(p-trifluoromethylphenyl)aluminum, trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum , tributylammonium tetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, diethylammoniumtetrapentafluorophene

Nylaluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammoniumtetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, triphenylcarboniumtetra(p -trifluoromethylphenyl) boron or triphenylcarbonium tetrapentafluorophenyl boron, etc. are mentioned.

The catalyst composition, as a first method, 1) contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 2 or Formula 3 to obtain a mixture; and 2) adding the compound represented by Formula 4 to the mixture.

In addition, the catalyst composition may be prepared by contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 4 as a second method.

In the case of the first method among the methods for preparing the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2/the compound represented by Formula 2 or Formula 3 is 1/ It may be 5,000 to 1/2, specifically 1/1,000 to 1/10, and more specifically 1/500 to 1/20. When the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 2 or Formula 3 exceeds 1/2, the amount of the alkylating agent is very small, and there is a problem that the alkylation of the metal compound cannot proceed completely, , when the molar ratio is less than 1/5,000, the metal compound is alkylated, but due to a side reaction between the remaining excess alkylating agent and the activator, which is the compound of Formula 4, there is a problem in that the activation of the alkylated metal compound cannot be completed. . In addition, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 4 may be 1/25 to 1, specifically 1/10 to 1, and more specifically 1/5 to can be 1. When the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 4 exceeds 1, the amount of the activator is relatively small, so the activation of the metal compound is not completely achieved, and thus the activity of the catalyst composition produced may fall, and when the molar ratio is less than 1/25, the metal compound is fully activated, but the unit price of the catalyst composition may not be economical or the purity of the resulting polymer may be deteriorated with an excess of the remaining activator.

In the case of the second method among the methods for preparing the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 4 may be 1/10,000 to 1/10, specifically 1/5,000 It may be 1/100 to 1/100, and more specifically, it may be 1/3,000 to 1/500. When the molar ratio exceeds 1/10, the amount of the activator is relatively small, so that the activation of the metal compound is not completely achieved, and thus the activity of the resulting catalyst composition may be decreased. When the molar ratio is less than 1/10,000, the activation of the metal compound is completely performed, but the cost of the catalyst composition may not be economical or the purity of the resulting polymer may be deteriorated with the excess amount of activator remaining.

In the preparation of the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene or toluene may be used as the reaction solvent.

In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a supported form on a carrier.

The carrier may be used without any particular limitation as long as it is used as a carrier in a metallocene-based catalyst. Specifically, the carrier may be silica, silica-alumina or silica-magnesia, and any one or a mixture of two or more thereof may be used.

Among them, when the carrier is silica, since the functional group of the silica carrier and the metallocene compound of Formula 1 chemically forms a bond, there is almost no catalyst released from the surface during olefin polymerization. As a result, it is possible to prevent the occurrence of fouling in which the reactor wall surface or polymer particles are agglomerated during the production process of the olefin-based polymer. In addition, the olefin-based polymer prepared in the presence of the catalyst including the silica carrier is excellent in particle shape and apparent density of the polymer.

More specifically, the carrier may be high-temperature dried silica or silica-alumina containing a siloxane group having high reactivity on the surface through a method such as high-temperature drying.

The carrier may further include an oxide, carbonate, sulfate or nitrate component such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ or Mg(NO ₃ ) ₂ .

The polymerization reaction for polymerizing the olefinic monomer may be performed by a conventional process applied to polymerization of the olefinic monomer, such as continuous solution polymerization, bulk polymerization, suspension polymerization, slurry polymerization, or emulsion polymerization.

The polymerization reaction of the olefin monomer may be performed under an inert solvent, and examples of the inert solvent include benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, but not limited thereto.

The polymerization of the olefin-based polymer may be carried out at a temperature of about 25 °C to about 500 °C, specifically 80 °C to 250 °C, more preferably at a temperature of 100 °C to 200 °C. In addition, the reaction pressure during polymerization is 1 kgf/cm ² to 150 kgf/cm ² , preferably 1 kgf/cm ² to 120 kgf/cm ² , more preferably 5 kgf/cm ² to 100 kgf/cm ² can be

On the other hand, the polypropylene-based composite material according to an embodiment of the present invention having the configuration as described above may include each component in an appropriate amount to satisfy its use and physical properties required accordingly. For example, in the present invention, the polypropylene-based composite material may include 5 wt% to 70 wt% of the (B) olefin-based polymer, specifically 10 wt% to 60 wt%, and more specifically 20 wt% to 50 wt% may be included.

When the content of the olefin-based polymer is less than the mixing ratio, there is a fear that impact strength may be lowered, and if it exceeds the mixing ratio, tensile strength and hardness may be reduced. The mixing ratio may be controlled in consideration of the remarkable physical properties of the polypropylene and the olefin-based polymer.

The polypropylene-based composite according to an embodiment of the present invention may further optionally include an inorganic filler together with the polypropylene and the olefin-based polymer to improve mechanical properties of the polypropylene-based composite.

Specifically, the inorganic filler may be a powder-type filler, a flake-type filler, a fibrous filler, or a balloon-type filler, and any one or a mixture of two or more thereof may be used. Specifically, the powdery filler includes natural silicic acid or silicate such as fine powder talc, kaolinite, calcined clay, and sericite; carbonates such as precipitated calcium carbonate, ground calcium carbonate or magnesium carbonate; hydroxides such as aluminum hydroxide or magnesium hydroxide; oxides such as zinc oxide, magnesium oxide, or titanium oxide; synthetic silicic acids or silicates such as hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid or silicic anhydride; Silicon carbide etc. are mentioned. In addition, the flaky filler may include mica. In addition, the fibrous filler may include basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processed Mineral Fiber), or potassium titanate. In addition, the balloon-type filler may include a glass balloon. The double may be talc.

In addition, the inorganic filler may be surface-treated to improve the strength characteristics and molding processability of the polypropylene composite.

Specifically, the surface may be physically or chemically surface-treated using a surface treatment agent such as a silane coupling agent, higher fatty acid, fatty acid metal salt, unsaturated organic acid, organic titanate, resin acid, or polyethylene glycol.

In addition, the inorganic filler may have an average particle diameter (D ₅₀ ) of 1 μm to 20 μm, specifically 3 μm to 15 μm, and more specifically 5 μm to 10 μm. If the average particle diameter of the inorganic filler is too small, it is difficult to uniformly disperse when mixed with polypropylene and olefin-based polymer due to aggregation between inorganic filler particles, and as a result, the effect of improving the mechanical properties of the polypropylene-based composite agent may be insignificant. In addition, if the average particle diameter of the inorganic filler is excessive, there is a risk of deterioration of the physical properties of the rubber composition due to the deterioration of the dispersibility of the inorganic filler itself.

In the present invention, the average particle diameter (D ₅₀ ) of the inorganic filler may be defined as a particle diameter based on 50% of the particle size distribution. In the present invention, the average particle diameter (D ₅₀ ) of the inorganic filler particles is, for example, a scanning electron microscope (scanning electron microscopy, SEM) or a field emission scanning electron microscope (field emission scanning electron microscopy, FE-SEM) using electrons, etc. It can be measured using microscopic observation or a laser diffraction method. When measuring by the laser diffraction method, more specifically, the inorganic filler particles are dispersed in a dispersion medium, and then introduced into a commercially available laser diffraction particle size measuring device (eg Microtrac MT 3000), and 50 of the particle size distribution in the measuring device The average particle diameter (D ₅₀ ) on a % basis can be calculated.

The inorganic filler may be included in an amount of 0.1 parts by weight to 40 parts by weight based on 100 parts by weight of polypropylene. If the content of the inorganic filler in the polypropylene composite is less than 0.1 parts by weight based on 100 parts by weight of polypropylene, the improvement effect due to the inclusion of the inorganic filler is insignificant, and if it exceeds 40 parts by weight, the processability of the polypropylene composite may be reduced. More specifically, the inorganic filler may be included in an amount of 0.1 wt% to 20 wt% based on the total weight of the polypropylene composite.

The polypropylene-based composite material according to an embodiment of the present invention satisfying the composition and content conditions as described above may be prepared by adding polypropylene and optionally an inorganic filler to the olefin-based polymer and then heat-treating. In this case, the type and content of the polypropylene are the same as described above.

The mixing process may be performed according to a conventional method. Specifically, the mixing may use a super mixer or a ribbon mixer.

In addition, additives such as antioxidants, heat stabilizers, UV stabilizers, and antistatic agents may be further included as needed during the mixing process. may be optionally further used in

In addition, the heat treatment process may be performed at a temperature greater than or equal to the melting point of polypropylene and less than or equal to 210°C. The heat treatment process is a conventional twin-screw extruder (twin-screw extruder), single-screw extruder (single-screw extruder), roll mill (roll-mill), kneader (kneader) or Banbury mixer (banbury mixer) using various compounding machines such as can be performed.

The polypropylene composite according to an embodiment of the present invention produced according to the manufacturing method as described above includes a low-density olefin-based polymer having a high crystallinity region introduced thereinto and exhibiting excellent mechanical rigidity, thereby exhibiting excellent polypropylene dispersibility. Also, as a result, it is possible to improve the mechanical properties without lowering the impact strength of the polypropylene composite.

Specifically, the polypropylene composite has a flexural strength of 180 kgf/cm ² to 500 kgf/cm ² , specifically 190 kgf/cm ² to 400 kgf/cm ² , when measuring flexural strength according to ASTM D790 Specifically, it may be 200 kgf/cm ² to 350 kgf/cm ² . In addition, the polypropylene-based composite material has a low-temperature impact strength of 20 kgf·m/m or more, specifically 20 kgf·m/m to 100 kgf·m/m, measured at room temperature (23° C.) by the ASTM D256 method, More specifically, it may be 30 kgf·m/m to 80 kgf·m/m.

Accordingly, the polypropylene-based composite material according to an embodiment of the present invention is hollow in various fields and uses, such as materials for automobiles, electric wires, toys, textiles, or medical products, for packaging, construction, and daily use. It is useful for molding, extrusion molding, or injection molding. In particular, it exhibits excellent impact strength at room temperature as well as low temperature, and has excellent physical properties such as heat resistance and rigidity, so it can be usefully used for interior and exterior parts of automobiles.

According to another embodiment of the present invention, there is provided a molded article and an automobile part manufactured using a polypropylene-based composite meeting the above-described physical property requirements.

Specifically, the molded article may be a blow molding molded article, an inflation molded article, a cast molded article, an extrusion laminate molded article, an extrusion molded article, an expanded molded article, an injection molded article, a sheet, a film, a fiber, a monofilament, or a nonwoven fabric.

In addition, the automobile parts may be interior/exterior materials for automobiles, and the like.

Example

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Synthesis of ligands and transition metal compounds

Organic reagents and solvents were purchased from Aldrich, and purified by standard methods unless otherwise specified. The reproducibility of the experiment was improved by blocking the contact of air and moisture at all stages of the synthesis.

Catalyst Preparation Example: Preparation of a transition metal compound

(1) Preparation of 2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline

(i) Preparation of lithium carbamate

2-Methylindoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were placed in a shlenk flask. The Schlenk flask was immersed in a -78°C low temperature bath made of dry ice and acetone and stirred for 30 minutes. Then, n-BuLi (39.3 mL, 2.5 M, 98.24 mmol) was injected into a syringe under a nitrogen atmosphere, and a pale yellow slurry was formed. Then, after stirring the flask for 2 hours, the temperature of the flask was raised to room temperature while removing the butane gas produced. The flask was again immersed in a low temperature bath at -78° C. to lower the temperature, and then CO ₂ gas was introduced. As the carbon dioxide gas was added, the slurry disappeared and became a transparent solution. The flask was connected to a bubbler and the temperature was raised to room temperature while removing carbon dioxide gas. After that, excess CO ₂ gas and solvent were removed under vacuum. After moving the flask to a dry box, pentane was added, stirred vigorously, and filtered to obtain lithium carbamate, a white solid compound. The white solid compound is coordinated with diethyl ether. In this case, the yield is 100%.

(ii) Preparation of 2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline

The lithium carbamate compound (8.47 g, 42.60 mmol) prepared in step (i) was placed in a Schlenk flask. Then, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were sequentially added. The Schlenk flask was immersed in a low temperature bath at -20°C made of acetone and a small amount of dry ice and stirred for 30 minutes, and then t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of the reaction mixture changed to red. Stirring was continued for 6 hours while maintaining -20°C. A solution of CeCl ₃ ·2LiCl dissolved in tetrahydrofuran (129 mL, 0.33 M, 42.60 mmol) and tetramethylcyclopentynone (5.89 g, 42.60 mmol) were mixed in a syringe, and then put into a flask under a nitrogen atmosphere. The temperature of the flask was slowly raised to room temperature, and after 1 hour, the thermostat was removed and the temperature was maintained at room temperature. Then, after adding water (15 mL) to the flask, ethyl acetate was added and filtered to obtain a filtrate. After transferring the filtrate to a separatory funnel, hydrochloric acid (2 N, 80 mL) was added thereto, and the mixture was shaken for 12 minutes. Then, after neutralization by adding a saturated aqueous sodium hydrogen carbonate solution (160 mL), the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to remove moisture, filtered, and the filtrate was taken to remove the solvent. The obtained filtrate was purified by column chromatography using a solvent of hexane and ethyl acetate (v/v, 10:1) to obtain an oily phase. The yield was 19%.

¹ H NMR(C ₆ D ₆ ): δ 6.97(d, J=7.2Hz, 1H, CH), δ 6.78(d, J=8Hz, 1H, CH), δ 6.67(t, J=7.4Hz, 1H) , CH), δ 3.94 (m, 1H, quinoline-CH), δ 3.51 (br s, 1H, NH), δ 3.24-3.08 (m, 2H, quinoline-CH ₂ , Cp-CH), δ 2.65 (m) , 1H, quinoline-CH ² ), δ 1.89(s, 3H, Cp-CH ₃ ), δ 1.84(s, 3H, Cp-CH ₃ ), δ 1.82(s, 3H, Cp-CH ₃ ), δ 1.13 (d, J=6Hz, 3H, quinoline-CH ₃ ), δ 0.93(3H, Cp-CH ₃ ) ppm.

(2) [(2-Methylindolin-7-yl)tetramethylcyclopentadienyl-eta5,kappa-N]titanium dimethyl ([(2-Methylindolin-7-yl)tetramethylcyclopentadienyl-eta5,kapa-N] production of titanium dimethyl)

(i) Preparation of [(2-methylindolin-7-yl)tetramethylcyclopentadienyl- η ⁵ , κ -N]dilithium compound

2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-indoline (2.25 g, 8.88 mmol) prepared through step (1) in a dry box and After putting 50 mL of diethyl ether into a round flask, the temperature was lowered to -30°C, and n-BuLi (4.9 g, 2.5 M, 17.8 mmol) was slowly added while stirring. The reaction was carried out for 6 hours while raising the temperature to room temperature. After that, it was filtered while washing with diethyl ether several times to obtain a solid. A vacuum was applied to remove the remaining solvent to obtain a dilithium salt compound coordinated with 0.58 equivalents of diethyl ether (1.37 g, 50%).

¹ H NMR (Pyridine-d8): δ 7.22 (br s, 1H, CH), δ 7.18 (d, J=6Hz, 1H, CH), δ 6.32 (t, 1H, CH), δ 4.61 (brs, 1H) , CH), δ 3.54 (m, 1H, CH), δ 3.00 (m, 1H, CH), δ 2.35-2.12 (m , 13H, CH, Cp-CH ₃ ), δ 1.39 (d, indoline-CH ₃ ) ) ppm.

(ii) (2-methylindolin-7-yl) tetramethylcyclopentadienyl- η ⁵ , κ -N] Preparation of titanium dimethyl

In a dry box, TiCl ₄ ·DME (1.24 g, 4.44 mmol) and diethyl ether (50 mL) were placed in a round flask, and while stirring at -30°C, MeLi (6.1 mL, 8.88 mmol, 1.4 M) was slowly added thereto. After stirring for 15 minutes, the [(2-methylindolin-7-yl)tetramethylcyclopentadienyl- η ⁵ , κ -N]dilithium compound prepared in step (i) (1.37 g, 4.44 mmol) was placed in the flask. While raising the temperature to room temperature, the mixture was stirred for 3 hours. After the reaction was completed, vacuum was applied to remove the solvent, dissolved in pentane, and filtered to obtain a filtrate. Vacuum was applied to remove pentane to give the title compound.

¹ H NMR (C ₆ D ₆ ): δ 7.01-6.96 (m, 2H, CH), δ 6.82 (t, J=7.4 Hz, 1H, CH), δ

4.96(m, 1H, CH), δ 2.88(m, 1H, CH), δ 2.40(m, 1H, CH), δ 2.02(s, 3H, Cp-CH ₃ ), δ 2.01(s, 3H, Cp -CH ₃ ), δ 1.70(s, 3H, Cp-CH ₃ ), δ 1.69(s, 3H, Cp-CH ₃ ), δ 1.65 (d, J=6.4Hz, 3H, indoline-CH ₃ ), δ 0.71 (d, J=10 Hz, 6H, TiMe ₂ -CH ₃ ) ppm.

Example Preparation Example 1: Preparation of olefin-based polymer

After the 1.5 L continuous process reactor was charged with hexane solvent (7 kg/h) and 1-butene (0.35 kg/h), the temperature at the top of the reactor was preheated to 139.0°C. 0.03 mmol/min of triisobutylaluminum compound (tiBAl), 0.20 μmol/min of the transition metal compound obtained in Preparation Example 1, and 0.60 μmol/min of the dimethylanilinium tetrakis (pentafluorophenyl) borate promoter were simultaneously charged into the reactor. was put in. Then, hydrogen gas (31 cc/min) and ethylene (0.87 kg/h) were introduced into the reactor and maintained at 139.0° C. for at least 30 minutes in a continuous process at a pressure of 89 bar to proceed with a copolymerization reaction to obtain a copolymer. . After drying in a vacuum oven for more than 12 hours, physical properties were measured.

Example Preparation Example 2: Preparation of olefin-based polymer

The copolymerization reaction was carried out in the same manner as in Preparation Example 1, and the amount of the transition metal compound, the amount of catalyst and co-catalyst, and the reaction temperature, the amount of hydrogen input, and the type and amount of the comonomer were changed as shown in Table 1 below to perform the copolymerization reaction. proceeded to obtain a copolymer.

Comparative Preparation Example 1

DF840 from Mitsui Chemicals was purchased and used.

Comparative Preparation Example 2

DF810 from Mitsui Chemicals was purchased and used.

Catalyst usage
(μmol
/min) cocatalyst
(μmol
/min) MMAO
(mmol
/min) ethylene
(kg/h) hexane
(Kg/h) 1-butene
(kg/h) Hydrogen
(cc/min) reaction temperature
(℃) Example Preparation Example 1 0.20 0.60 0.03 0.87 7 0.35 31 139.0 Example Preparation 2 0.29 0.87 0.03 0.87 7 0.29 33 140.2

Experimental Example 1: Evaluation of physical properties of olefin-based polymers

The physical properties of the copolymers of Preparation Examples 1 and 2 and Comparative Preparation Examples 1 and 2 were evaluated according to the following method, and are shown in Table 2 below.

1) Density of the polymer

Measured by ASTM D-792.

2) Melt Index (MI) of polymer

It was measured by ASTM D-1238 (Condition E, 190°C, 2.16 kg load).

3) Melt flow rate ratio (MFRR)

After measuring MI10 and MI2.16 according to ASTM D-1238 [Condition E, MI10 (190°C, 10 kg load), MI2.16 (190°C, 2.16 kg load)], divide MI10 by MI2.16 and melt flow rate The ratio (MFRR) was calculated.

4) Weight average molecular weight (Mw, g/mol) and molecular weight distribution (MWD)

The number average molecular weight (Mn) and the weight average molecular weight (Mw) were respectively measured using gel permeation chromatography (GPC), and the molecular weight distribution was calculated by dividing the weight average molecular weight by the number average molecular weight.

- Column: PL Olexis

- Solvent: TCB (Trichlorobenzene)

- Flow rate: 1.0 ml/min

- Sample concentration: 1.0 mg/ml

- Injection volume: 200 μl

- Column temperature: 160℃

- Detector: Agilent High Temperature RI detector

- Standard: Polystyrene (corrected by cubic function)

5) Melting point (Tm) and glass transition temperature (Tg)

It was obtained using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 250) manufactured by TA Instruments. That is, after the temperature was increased to 150°C, the temperature was maintained at that temperature for 1 minute, then lowered to -100°C, and the temperature was increased again to observe the DSC curve.

6) T(90), T(50) dH(100), and dH(90)

The differential scanning calorimeter (DSC: Differential Scanning Calorimeter 250) manufactured by TA Instruments was obtained by SSA (Successive self-nucleation/annealing) measurement method.

Specifically, in the first cycle, the temperature was increased to 150°C, held at that temperature for 1 minute, and then cooled to -100°C. In the second cycle, the temperature was increased to 120 °C, held at that temperature for 30 minutes and then cooled to -100 °C. In the third cycle, the temperature was increased to 110 °C, held at that temperature for 30 minutes and then cooled to -100 °C. In this way, the process of raising the temperature at 10°C intervals and cooling to -100°C was repeated until -60°C so that crystallization was performed for each temperature section.

In the last cycle, the heat capacity was specified while increasing the temperature to 150°C.

The temperature-heat capacity curve obtained in this way was integrated for each section to fractionate the heat capacity of each section compared to the total heat capacity. Here, the temperature at which 50% of the total is melted is defined as T(50), and the temperature at which 90% is melted is defined as T(90).

In addition, when measuring SSA, the melting enthalpy (ΔH) at 90°C or higher was defined as dH(90), and the melting enthalpy (ΔH) at 100°C or higher was defined as dH(100).

1 shows a graph as a result of measuring the polymers of Preparation Example 2 and Comparative Preparation Example 2 by differential scanning calorimetry (SSA).

density
(g/mL) MI
(g/
10min) MFRR Tg
(℃) Mw
(g/mol) MWD SSA Tm
(℃) T(50) T(90) T(90)-T(50) dH(100)
(J/g) dH(90)
(J/g) Example Preparation Example 1 0.8880 3.21 6.48 -44.8 86057 2.10 71.1 68.1 90.1 22.0 1.82 4.25 Example Preparation 2 0.8850 1.16 6.53 -43.1 108628 2.03 70.6 66.9 84.4 17.5 0.98 1.63 Comparative Preparation Example 1 0.8840 3.44 6.31 -42.9 83425 1.93 70.9 56.0 76.7 20.7 0 0 Comparative Preparation Example 2 0.8840 1.18 6.51 -43.3 114216 1.90 69.3 58.1 77.8 19.7 0 0

Referring to Table 2, the olefin-based polymers of Preparation Examples 1 and 2 satisfy the requirements (1) to (5) of the olefin-based polymer and of Comparative Preparation Examples 1 and 2 having the same level of density and MI. Compared to the olefinic polymers, respectively, they exhibited small T(90)-T(50) values. In particular, the olefinic polymers of Preparation Examples 1 and 2 satisfy the requirements of 0.5 J/g≤dH(100)≤3.0 J/g and 1.0 J/g≤dH(90)≤6.0 J/g, but compared In the olefin-based polymer of Preparation Example 2, both dH(100) and dH(90) showed a value of 0, which was not satisfied.

Meanwhile, FIG. 1 shows graphs of the results of measurement by differential scanning calorimetry (SSA) for the olefin-based polymers of Preparation Example 1 and Comparative Preparation Example 2.

Referring to FIG. 2 , it can be seen that the olefin-based polymer of Preparation Example 2 is eluted at a higher overall temperature than the olefin-based polymer of Comparative Preparation Example 2. Through this, it can be confirmed that the high crystallinity region is introduced in the olefin-based polymer of Preparation Example 2, and when the high crystallinity region is introduced in this way, the olefin-based polymer may exhibit high tensile strength and hardness.

Example 1: Preparation of polypropylene-based composites

30 parts by weight of the olefin copolymer prepared in Example 1, 30 parts by weight of a high crystalline impact copolymer polypropylene (CB5230, manufactured by Daehan Petrochemical) having a melt index (230° C., 2.16 kg) of 30 g/10 min, 30 parts by weight of high crystalline impact copolymer polypropylene (CB5290, manufactured by Korea Petrochemical Co., Ltd.) having a melt index (230° C., 2.16 kg) of 90 g/10 min, and talc (KCM6300, Kotsu Corporation) (average particle diameter (D ₅₀ )= 5.5 μm) 10 parts by weight, 0.1 parts by weight of Songnox1010 (manufactured by Songwon Industrial Co., Ltd.), 0.1 parts by weight of tris(2,4-di-tert-butylphenyl)phosphite (Songnox1680, manufactured by Songwon Industrial Co., Ltd.) as antioxidants, and calcium 0.3 parts by weight of stearate (Ca-st) was added, and then melt-kneaded using a twin-screw extruder to prepare a polypropylene-based composite compound in the form of pellets. At this time, the twin screw extruder had a diameter of 25Φ, a ratio of diameter and length of 40, a barrel temperature of 200°C to 230°C, a screw rotation speed of 250 rpm, and an extrusion amount of 18 kr/hr.

Examples 2 to 6: Preparation of polypropylene-based composites

Except that the type and content of the olefin copolymer, the content of polypropylene, and the content of talc were used differently as shown in Table 3 instead of the olefin copolymer prepared in Example 1, Example 1 and A polypropylene-based composite was prepared in the same manner.

Comparative Examples 1 to 6: Preparation of polypropylene-based composites

Except that the type and content of the olefin copolymer, the content of polypropylene, and the content of talc were used differently as shown in Table 3 instead of the olefin copolymer prepared in Example 1, Example 1 and A polypropylene-based composite was prepared in the same manner.

olefinic
polymer polypropylene talc type content
(parts by weight) CB5230
(parts by weight) CB5290
(parts by weight) content
(parts by weight) Example 1 Example Preparation Example 1 30 30 30 10 Example 2 Example Preparation 2 30 30 30 10 Example 3 Example Preparation Example 1 30 0 60 10 Example 4 Example Preparation 2 30 0 60 10 Example 5 Example Preparation Example 1 40 20 20 20 Example 6 Example Preparation 2 40 20 20 20 Comparative Example 1 Comparative Preparation Example 1 30 30 30 10 Comparative Example 2 Comparative Preparation Example 2 30 30 30 10 Comparative Example 3 Comparative Preparation Example 1 30 0 60 10 Comparative Example 4 Comparative Preparation Example 2 30 0 60 10 Comparative Example 5 Comparative Preparation Example 1 40 20 20 20 Comparative Example 6 Comparative Preparation Example 2 40 20 20 20

Experimental Example 2: Evaluation of physical properties of polypropylene-based composites

In order to confirm the physical properties of the polypropylene-based composites prepared in Examples 1 to 6 and Comparative Examples 1 to 6, the polypropylene-based composite was prepared by injection molding at a temperature of 230° C. using an injection machine, and the specimen was prepared at a constant temperature. After standing in a humidity room for more than 36 hours, the flexural strength and impact strength of the polymer were measured. The physical properties of the prepared specimens are shown in Table 6 below.

1) Flexural strength

After aging by standing in a constant temperature and humidity room (23° C., 50%) for more than 36 hours, it was measured according to ASTM D790 using an INSTRON 3365 device.

2) Impact strength

It was carried out according to ASTM D256, and after aging at room temperature (23° C.) for more than 6 hours, the impact strength at room temperature was measured.

olefinic
polymer polypropylene talc flexural strength
(kgf/cm ² ) room temperature impact strength
(kgf m/m) type content
(parts by weight) CB5230
(parts by weight) CB5290
(parts by weight) content
(parts by weight) Example 1 Example Preparation Example 1 30 30 30 10 299 48.0 Example 2 Example Preparation 2 30 30 30 10 309 39.5 Example 3 Example Preparation Example 1 30 0 60 10 283 41.8 Example 4 Example Preparation 2 30 0 60 10 291 32.7 Example 5 Example Preparation Example 1 40 20 20 20 209 66.0 Example 6 Example Preparation 2 40 20 20 20 214 63.2 Comparative Example 1 Comparative Preparation Example 1 30 30 30 10 289 48.2 Comparative Example 2 Comparative Preparation Example 2 30 30 30 10 295 39.1 Comparative Example 3 Comparative Preparation Example 1 30 0 60 10 272 41.0 Comparative Example 4 Comparative Preparation Example 2 30 0 60 10 281 33.2 Comparative Example 5 Comparative Preparation Example 1 40 20 20 20 200 66.3 Comparative Example 6 Comparative Preparation Example 2 40 20 20 20 203 62.3

Referring to Table 4, when comparing the polypropylene-based composites prepared by using the olefin-based copolymer having the same level of density and MI value, the olefin-based copolymer, the polypropylene-based polymer and the inorganic filler content are compared, It can be seen that the polypropylene-based composites of Examples 1 to 6 exhibit more improved flexural strength while having a similar level of room temperature impact strength compared to the polypropylene-based composites of Comparative Examples 1 to 6.

Through these results, it can be confirmed that the polypropylene-based composite of Examples includes an olefin-based copolymer having a high crystallinity region and exhibiting excellent mechanical rigidity, thereby increasing the mechanical rigidity of the polypropylene-based composite.

Claims (18)

(A) polypropylene, and
(B) a polypropylene-based composite comprising an olefin-based polymer satisfying the requirements of (1) to (5) below:
(1) Melt index (MI, 190 °C, 2.16 kg load condition): 0.1 to 10.0 g/10 min;
(2) density (d): 0.875 to 0.895 g/cc;
(3) 0.5 J/g≤dH(100)≤3.0 J/g, and 1.0 J/g≤dH(90)≤6.0 J/g when measured by differential scanning calorimetry (SSA);
(4) 15≤T(90)-T(50)≤30 in differential scanning calorimetry precision measurement (SSA), and 50°C≤T(50)≤75°C;
(5) Melting point (Tm) measured by differential scanning calorimetry (DSC) is 55℃≤Tm≤80℃
Here, T(50) and T(90) are the temperatures at which 50% and 90% of each is melted when the temperature-heat capacity curve is fractionated from the differential scanning calorimetry precision measurement (SSA) measurement result, respectively, and dH(90) is It is the enthalpy of melting at 90°C or higher, and dH(100) represents the melting enthalpy at 100°C or higher.
The method of claim 1,
The (A) polypropylene is a polypropylene-based composite material having a melt index of 0.5 g/10min to 100 g/10min measured at 230°C and a load of 2.16 kg.
The method of claim 1,
The (A) polypropylene is a polypropylene-based composite material having a melt index of 0.5 g/10 min to 100 g/10 min measured at 230°C and a load of 2.16 kg.
The method of claim 1,
The (B) olefin-based polymer further satisfies the requirement that (6) a glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) is -70°C≤T(50)≤-43°C. .
The method of claim 1,
The (B) olefin-based polymer further satisfies the requirement of (7) a weight average molecular weight (Mw) of 10,000 g/mol to 500,000 g/mol.
The method of claim 1,
The (B) olefin-based polymer further satisfies (8) a molecular weight distribution (MWD, molecular weight density) requirement of 0.1 to 6.0.
The method of claim 1,
The (B) olefin-based polymer further satisfies the requirement of (9) a melt flow rate ratio (MFRR) of 5 to 10.
The method of claim 1,
The (B) olefin-based polymer is a polypropylene-based polymer wherein T(90)-T(50) is 16≤T(90)-T(50)≤25, and 52℃≤T(50)≤74℃ composites.
The method of claim 1,
The olefin-based polymer is a polypropylene-based composite wherein the dH (100) and dH (90) are 0.9≤dH(100)≤2.0, and 1.5≤dH(90)≤5.0.
The method of claim 1,
The (B) olefin-based polymer is a polypropylene-based composite that is a copolymer of ethylene and an alpha-olefin comonomer having 3 to 12 carbon atoms.
11. The method of claim 10,
The alpha-olefin comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene , 1-tetradecene, 1-hexadecene, 1-itocene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1,5 - A polypropylene-based composite comprising any one or a mixture of two or more selected from the group consisting of pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.
The method of claim 1,
The (B) olefin-based polymer is a polypropylene-based composite material that is a copolymer of ethylene and 1-butene.
The method of claim 1,
The (B) olefin-based polymer is obtained by a manufacturing method comprising the step of polymerizing an olefin-based monomer by introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of Formula 1 below. Propylene-based composites:
[Formula 1]

In Formula 1,
R ₁ is the same as or different from each other, and each independently represents a Group 4 metal substituted with hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl, silyl, alkylaryl, arylalkyl, or hydrocarbyl. a metalloid radical, wherein the two R ₁ may be connected to each other by an alkylidine radical including an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms to form a ring;
R ₂ are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; aryl; alkoxy; aryloxy; an amido radical, wherein two or more of R ₂ may be connected to each other to form an aliphatic ring or an aromatic ring;
R ₃ are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; or an aliphatic or aromatic ring containing nitrogen, substituted or unsubstituted with an aryl radical, and when the substituents are plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;
M is a Group 4 transition metal;
Q ₁ and Q ₂ are each independently halogen; alkyl having 1 to 20 carbon atoms; alkenyl; aryl; alkylaryl; arylalkyl; alkyl amido having 1 to 20 carbon atoms; aryl amido; or an alkylidene radical having 1 to 20 carbon atoms.
14. The method of claim 13,
The amount of the hydrogen gas is 0.35 to 3.00 parts by weight based on 1 part by weight of the olefinic monomer added to the reaction system.
14. The method of claim 13,
The (B) olefin-based polymer is a polypropylene-based composite prepared by a continuous solution polymerization reaction using a continuous stirred tank reactor (Continuous Stirred Tank Reactor) by introducing hydrogen gas in the presence of the catalyst composition for olefin polymerization.
The method of claim 1,
The polypropylene-based composite is a polypropylene-based composite comprising 5 to 70% by weight of the (B) olefin-based polymer.
The method of claim 1,
The polypropylene-based composite is a polypropylene-based composite further comprising an inorganic filler.
18. The method of claim 17,
The polypropylene-based composite includes (A) the inorganic filler in an amount of 0.1 parts by weight to 40 parts by weight based on 100 parts by weight of polypropylene,
The inorganic filler is a polypropylene-based composite having an average particle diameter (D ₅₀ ) of 1 μm to 20 μm.

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