KR101642505B1 - Method for preparing propylene-1-butene copolymer resin composition and propylene-1-butene copolymer resin composition prepared therefrom - Google Patents

Abstract

The present invention relates to a process for producing a propylene-1-butene copolymer resin composition and a propylene-1-butene copolymer resin composition obtained therefrom. More particularly, the present invention relates to a process for producing a propylene-1-butene copolymer resin composition using a catalyst and a nucleating agent containing a novel metallocene compound having an excellent copolymerization activity, and a propylene-1-butene copolymer resin composition .
According to the present invention, by copolymerizing propylene and 1-butene using a novel metallocene compound having excellent copolymerization activity and hydrogen reactivity, it is possible to easily control physical properties of a copolymer and to obtain propylene-1-butene copolymer The merger can be obtained.

Description

TECHNICAL FIELD The present invention relates to a propylene-1-butene copolymer resin composition and a propylene-1-butene copolymer resin composition and a propylene-1-butene copolymer resin composition prepared therefrom,

The present invention relates to a process for producing a propylene-1-butene copolymer and a propylene-1-butene copolymer obtained therefrom. More specifically, the present invention relates to a process for producing a propylene-1-butene copolymer using a catalyst containing a novel metallocene compound having an excellent copolymerization activity and a propylene-1-butene copolymer obtained therefrom.

Dow has announced the early 1990s [Me ₂ Si (Me ₄ C ₅ ) NtBu] TiCl ₂ (hereinafter abbreviated as CGC) (U.S. Patent No. 5,064,802) - In the copolymerization of olefins, the CGC is superior to conventional metallocene catalysts in two major ways: (1) high molecular weight polymers with high activity even at high polymerization temperatures; , And (2) the copolymerization of alpha-olefins with large steric hindrance such as 1-hexene and 1-octene is also excellent. In addition, various characteristics of CGC were gradually known during the polymerization reaction, and efforts to synthesize the derivative and use it as a polymerization catalyst have actively been made in academia and industry.

A Group 4 transition metal compound having one or two cyclopentadienyl groups as ligands can be activated with methylaluminoxane or a boron compound to be used as a catalyst for olefin polymerization. These catalysts exhibit unique properties that conventional Ziegler-Natta catalysts can not achieve.

That is, the polymer obtained using such a catalyst has a narrow molecular weight distribution and better reactivity with the second monomer such as alpha olefin or cyclic olefin, and the second monomer distribution of the polymer is uniform. Further, by changing the substituent of the cyclopentadienyl ligand in the metallocene catalyst, the stereoselectivity of the polymer can be controlled when the alpha olefin is polymerized, and the degree of copolymerization, the molecular weight, and the molecular weight of the second monomer Distribution and the like can be easily controlled.

On the other hand, since metallocene catalysts are more expensive than conventional Ziegler-Natta catalysts, they are economically worthy of good activity. If the reactivity to the second monomer is good, there is an advantage that a polymer containing a large amount of the second monomer can be obtained even by introducing a small amount of the second monomer.

A number of researchers have studied various catalysts, and it has generally been found that the bridged catalyst is more reactive to the second monomer. The bridged catalyst studied so far can be roughly classified into three types according to the bridge type. One is a catalyst in which two cyclopentadienyl ligands are linked by an alkylene di-bridge through the reaction of an electrophile such as an alkyl halide with indene or fluorene, the second is a silicon bridged catalyst connected by -SiR ₂ - Is a methylene bridged catalyst obtained from the reaction of fulvene with indene or fluorene.

However, among the above attempts, the catalysts actually applied to commercial plants are few, and the production of catalysts showing improved polymerization performance is still required.

In addition, when the metallocene compound is applied to a commercial commercialized gas phase and slurry plant, the carrier is supported. Studies have been made to carry out co-catalysis at the same time to carry out the catalytic reaction and to exhibit activity without addition of additional co-catalyst during the polymerization process. However, if a non-homogeneous catalyst is prepared by carrying out basically, The activity becomes lower than that of the homogeneous catalyst.

US Patent No. 5,064,802

In order to solve the above-mentioned problems, the present invention provides a process for producing a propylene-1-butene copolymer by polymerizing propylene and 1-butene in the presence of a catalyst comprising a metallocene compound having a novel structure, And a step of extruding the propylene-1-butene copolymer by adding a nucleating agent to the propylene-1-butene copolymer.

The present invention also provides a propylene-1-butene copolymer resin composition obtained by the above production method.

The present invention relates to a process for producing propylene-1-butene copolymer by polymerizing propylene and 1-butene in the presence of a catalyst comprising a metallocene compound represented by the following formula (1): And

And a step of adding a nucleating agent to the propylene-1-butene copolymer and extruding the propylene-1-butene copolymer.

[Chemical Formula 1]

In Formula 1,

M ¹ is a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide series transition metal or an ethanide series transition metal;

X is the same or different halogen;

A is a bridge group connecting an indenyl group as an element of Group 14;

R ¹ is alkyl, alkenyl, alkylaryl, arylalkyl or aryl of 1 to 20 carbon atoms;

R ² is hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl, alkylaryl, arylalkyl or aryl;

R ³ , R ^{3 '} , R ⁴ , and R ^4' are the same or different from each other and are each an alkyl, alkenyl, alkylaryl, arylalkyl, or aryl having 1 to 20 carbon atoms;

n is an integer of 1 to 20;

The present invention also provides a propylene-1-butene copolymer obtained by the above production method.

According to the process for producing a propylene-1-butene copolymer according to the present invention, propylene and 1-butene are copolymerized using a novel metallocene compound having excellent copolymerization activity and hydrogen reactivity to obtain a propylene- A propylene-1-butene copolymer resin composition is obtained by adding a nucleating agent to the propylene-1-butene copolymer and extruding it, thereby easily controlling the physical properties of the copolymer and having excellent mechanical properties.

Further, the resin composition obtained by the process for producing a propylene-1-butene copolymer resin composition according to the present invention shows high transparency and is excellent in mechanical properties, fluidity and crystallinity, and can be used for various purposes.

Hereinafter, a method for producing a propylene-1-butene copolymer resin composition according to a specific embodiment of the present invention and a propylene-1-butene copolymer resin composition obtained by the above production method will be described in more detail. It is to be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

In addition, throughout this specification, "comprising" or "containing ", unless specifically stated, refers to including any and all components (or components) Can not be interpreted as excluding.

According to one aspect of the present invention, there is provided a process for producing a propylene-1-butene copolymer, which comprises polymerizing propylene and 1-butene in the presence of a catalyst comprising a metallocene compound represented by the following formula (1) And

And a step of adding a nucleating agent to the propylene-1-butene copolymer and extruding the propylene-1-butene copolymer.

[Chemical Formula 1]

In Formula 1,

M ¹ is a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide series transition metal or an ethanide series transition metal;

X is the same or different halogen;

A is a bridge group connecting an indenyl group as an element of Group 14;

R ¹ is alkyl, alkenyl, alkylaryl, arylalkyl or aryl of 1 to 20 carbon atoms;

R ² is hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl, alkylaryl, arylalkyl or aryl;

R ³ , R ^{3 '} , R ⁴ , and R ^4' are the same or different from each other and are each an alkyl, alkenyl, alkylaryl, arylalkyl, or aryl having 1 to 20 carbon atoms;

n is an integer of 1 to 20;

Preferably, R ¹ and R ² in the general formula (1) are each alkyl having 1 to 4 carbon atoms; R ³ and R ^{3 '} are each alkyl, alkenyl, or arylalkyl having 1 to 20 carbon atoms; R ⁴ and R ^{4 '} are each aryl or alkylaryl of 1 to 20 carbon atoms; n is an integer from 1 to 6; A may be silicon (Si).

The metallocene compound of Formula 1 has two indenyl groups in which a substituent other than hydrogen is introduced at the 2-position and the 4-position as a ligand, and in particular, a bridge group group is substituted with a functional group capable of acting as a Lewis base as an oxygen-donor, thereby maximizing the activity as a catalyst. And exhibits high polymerization activity even when carried on a carrier. Accordingly, when the compound of Formula 1 is supported on its own or on a carrier and used as a catalyst in the production of polyolefins, a polyolefin having desired properties can be more easily produced.

According to one embodiment of the present invention, the metallocene compound represented by Formula 1 may be used alone or in a step of preparing a propylene-1-butene copolymer as a supported catalyst supported on a support together with a cocatalyst . The cocatalyst may include an alkylaluminoxane-based cocatalyst, and a boron-based cocatalyst.

The carrier may be any of those generally used in the technical field to which the present invention belongs, so that it is not particularly limited, but preferably at least one carrier selected from the group consisting of silica, silica-alumina and silica-magnesia may be used. On the other hand, when supported on a support such as silica, since the silica carrier and the functional group of the metallocene compound are chemically bonded and supported, there is almost no catalyst liberated from the surface of the support in the olefin polymerization process. Butene copolymer does not cause fouling on the wall surface of the reactor or the polymer particles.

The propylene-1-butene copolymer produced in the presence of the supported catalyst containing such a carrier is excellent in particle shape and bulk density of the polymer and can be suitably used for conventional slurry polymerization or bulk polymerization and gas phase polymerization processes Do.

Therefore, it is preferable to use a carrier which is dried at a high temperature and has a siloxane group having high reactivity on the surface. Specifically, silica, silica was dried at high temperature - can be used are alumina and the like, which are typically _{Na 2 O, K 2 CO 3} , BaSO 4, Mg (NO 3) an oxide of _2, such as carbonate, sulfate, nitrate component .

According to one embodiment of the present invention, the metallocene compound represented by Formula 1 may be used as a catalyst for propylene and 1-butene polymerization together with an alkylaluminoxane-based co-catalyst and a boron-based co-catalyst.

The alkylaluminoxane-based co-catalyst may be represented by the following formula (2).

(2)

In Formula 2,

M ² is a Group 13 metal element;

R ⁵ are the same or different and are each an alkyl, alkenyl, alkylaryl, arylalkyl or aryl having 1 to 20 carbon atoms;

m may be an integer of 2 or more.

The alkylaluminoxane-based promoter is preferably a compound wherein R ⁵ in the above formula 2 is methyl, ethyl, propyl, isopropyl, isopropenyl, n- butyl (n-butyl), sec- butyl (sec -butyl), tert- butyl (tert -butyl), pentyl (pentyl), hexyl (hexyl), octyl (octyl), decyl (decyl), dodecyl (dodecyl) Tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, eikosyl, dokosyl, tetrakosyl, cyclododecyl, cyclohexyl, Cyclohexyl, cyclooctyl, phenyl, tolyl, or ethylphenyl; M ² may be aluminum.

In Formula 2, m may be an integer of 2 or more, or an integer of 2 to 500, preferably 6 or more, or an integer of 6 to 300, more preferably 10 or more, or an integer of 10 to 100 .

The alkylaluminoxane-based co-catalyst may be a compound capable of acting as a Lewis acid capable of forming a bond through a Lewis acid-base interaction with a functional group introduced into a bridge group of the metallocene compound of Formula 1 And a metal element. The promoter compound of Formula 2 may exist in a linear, circular or network form. Examples of the promoter compound include at least one of methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane and butyl aluminoxane. have.

In addition, in the catalyst for propylene-1-butene copolymerization of the present invention, as the alkylaluminoxane-based co-catalyst, a non-alkylaluminoxane-based co-catalyst containing a non-conjugated anion may be used. In particular, according to an embodiment of the present invention, a boron-based promoter may be used as the non-alkylaluminoxane-based co-catalyst.

The boron-based promoter may be selected from the group consisting of dimethylanilinium tetrakis (pentafluorophenyl) borate, [HN (CH ₃ ) ₂ C ₆ H ₅ ] [B (C ₆ F ₅ ) ₄ ] ), Trityl tetakis (pentafluorophenyl) borate, [(C ₆ H ₅ ) ₃ C] [B (C ₆ F ₅ ) ₄ ]), and methyl anilinium tetrakis (Pentafluorodiphenyl) borate, [HN (CH ₃ ) (C ₆ H ₅ ) ₂ ] [B (C ₆ F ₅ ) ₄ ] Can be used.

The boron-based promoter enables stabilization of the metallocene compound to maintain activity in the polymerization. In particular, the metallocene compound used in the present invention has a tether, and leaching phenomenon does not occur due to the functional group, so that fouling does not occur and excellent activity can be exhibited. However, if there is no tether such as a known metallocene compound, there is a problem that fouling occurs mostly due to reaction with a leached catalyst precursor and a boron-based co-catalyst.

In the production process of the present invention, two promoters of an alkylaluminoxane-based promoter and a non-alkylaluminoxane-based boron-based promoter can be simultaneously carried to form a supported catalyst having improved activity. Also, the co-catalysts which did not cause adverse effects between the two co-catalysts were selected, and the optimum supporting ratio was confirmed through experiments.

In the process for preparing a propylene-1-butene copolymer according to an embodiment of the present invention, the metallocene compound is present in an amount of from about 40 to about 240 micromoles, preferably from about 80 to about 250 micromoles, And can be carried in a content range of about 160 μmol.

In addition, the alkylaluminoxane-based cocatalyst may be supported in an amount of about 8 to about 25 mmol, preferably about 10 to about 20 mmol, based on 1 g of silica per weight of carrier, for example, 1 g of silica.

The boron based promoter may be supported in an amount ranging from about 50 to about 300 μmol, preferably about 64 to about 240 μmol, based on 1 g of silica per weight of carrier, based on 1 g of silica.

In the process for producing a propylene-1-butene copolymer resin composition according to an embodiment of the present invention. The catalyst has an improved catalytic activity over the supported catalyst having one kind of promoter, and even if the supporting condition of the metallocene compound is changed, that is, the reaction temperature, the reaction time, the type of silica and the loading amount of the metallocene compound Propene-1-butene copolymer can be produced with improved activity.

Here, the polymerization of propylene and 1-butene can be carried out by reacting at a temperature of about 25 ° C to about 500 ° C and a pressure of about 1 to about 100 kgf / cm ² for about 1 to about 24 hours. At this time, the polymerization reaction temperature is preferably about 25 ° C to about 200 ° C, and more preferably about 50 ° C to about 100 ° C. Further, the polymerization reaction pressure is preferably about 1 to about 70 kgf / cm ² , more preferably about 5 to about 50 kgf / cm ² . The polymerization reaction time is preferably about 1 to about 5 hours.

In the present invention, the step of preparing the propylene-1-butene copolymer may be carried out by contacting the catalyst containing the metallocene compound represented by the above formula (1) with propylene and 1-butene.

The propylene and 1-butene may be polymerized in a ratio of about 99.5: 0.5 to about 85:15, preferably about 99: 1 to about 90:10, but are not limited thereto.

Further, according to one embodiment of the present invention, the polymerization of propylene and 1-butene can be carried out under hydrogen gas.

At this time, the hydrogen gas activates the inactive sites of the metallocene catalyst and causes a chain transfer reaction to control the molecular weight. The metallocene compound of the present invention is excellent in hydrogen reactivity, and therefore, by controlling the amount of hydrogen gas used in the polymerization step, a propylene-1-butene copolymer having a desired molecular weight distribution can be effectively obtained.

The hydrogen gas may be added in an amount of about 10 to about 2000 ppm, preferably about 50 to about 1500 ppm, based on the total content of propylene. It is possible to control the molecular weight distribution and the fluidity of the propylene-1-butene copolymer which is produced while exhibiting sufficient catalytic activity by controlling the use amount of the hydrogen gas. Thus, propylene-1-butene copolymer Butene copolymer can be produced.

The propylene-1-butene copolymer may be prepared by a solution polymerization process, a slurry process or a gas phase process using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor, and the like.

In the method for producing a propylene-1-butene copolymer resin composition according to the present invention, the catalyst may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the polymerization of an olefin monomer, for example, pentane, hexane, heptane, Decane, an isomer thereof and an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene, or the like. It is preferable to use a small amount of water or air, which acts as a catalyst poison, by using a small amount of alkylaluminum.

Meanwhile, the process for producing the propylene-1-butene copolymer resin composition of the present invention comprises the step of adding a nucleating agent to the propylene-1-butene copolymer prepared through the step of producing the propylene-1-butene copolymer and extruding .

The nucleating agent may act to inhibit dispersion by light by making the crystallite size of the resin small at the step of extruding together with the propylene-1-butene copolymer, and the propylene-1-butene copolymer resin composition Transparency and fluidity can be improved.

As such a nucleus agent, a carbon-based compound can be used. Specifically, Millad 3988 (manufacturer: Milliken), NX8000 (manufacturer: Milliken) and NU700 (manufacturer: Dongbu Chemical), which are carbon- have. In the process for producing a propylene-1-butene copolymer resin composition of the above embodiment, it is preferable to include NU700 which is inexpensive and has high transparency.

The nucleating agent may contain about 2000 to about 3000 ppm, and preferably about 2200 to 2500 ppm, based on the weight of the propylene-1-butene copolymer. When the content of the nucleating agent is too small, the effect of improving transparency and fluidity due to the addition of the nucleating agent may be insignificant. In view of economical efficiency of the process, it is preferable that the nucleating agent is contained in the above range.

In addition, in the step of adding the nucleating agent to the propylene-1-butene copolymer and extruding the propylene-1-butene copolymer, an additive may be further added in addition to the nucleating agent.

Antioxidants, slip agents, anti-blocking agents, UV stabilizers, antistatic agents and the like may be optionally used as the additive within the range not deviating from the object of the present invention. These additives may be propylene-1-butene About 500 to 2500 ppm, preferably about 500 to 1500 ppm, based on the weight of the copolymer.

The propylene-1-butene copolymer resin composition can be produced by using an extrusion process known to be commonly used, without limitation, for example, by using an extruder such as Haake Rheocord, Leistritz, The propylene-1-butene copolymer resin composition can be prepared at 100 to 1000 rpm.

According to another aspect of the present invention, there is provided a propylene-1-butene copolymer resin composition obtained by the above-described production method.

As described above, according to the present invention, by using the catalyst and the nucleating agent containing the novel metallocene compound, propylene-1-butene having high transparency and high flowability as compared with the case of using the existing metallocene compound A copolymer resin composition can be obtained.

remind The propylene-1-butene copolymer may be a random copolymer. The random copolymer can be used for a packaging container, a film, a sheet, an injection-molded product, and the like which are required to have transparency because the processing temperature is low and transparency and fluidity are excellent.

According to an embodiment of the present invention, a propylene-1-butene copolymer prepared by preparing a propylene-1-butene copolymer using the catalyst containing the metallocene compound, The resin composition may have a haze value measured at intervals of 1 mm according to ASTM D1003 of 10% or less and a haze value measured at intervals of 2 mm may be 20% or less.

The propylene-1-butene copolymer may have a flexural modulus value according to ASTM D790 of about 10,000 kgf / cm2 or more, and preferably about 11000 to 16000 kgf / cm2.

The propylene-1-butene copolymer may have an IZOD impact strength value according to ASTM D256A of about 2.5 kgfcm / cm or more, and preferably about 3.0 to 4.0 kgfcm / cm.

On the other hand, when the polymerization process of propylene and 1-butene is carried out using the catalyst containing the metallocene compound, the resulting propylene-1-butene copolymer has a weight average molecular weight (Mw) of about 50,000 to about 500,000 g / mol, preferably from about 100,000 to about 300,000 g / mol.

The propylene-1-butene copolymer thus produced may have a molecular weight distribution (Mw / Mn) of about 1 to about 5, preferably about 2 to about 3.5.

In addition, Propene-1-butene copolymer has a 1-butene content of from about 0.5 to about 15 wt%, preferably from about 1 to about 10 wt%, based on the weight of the total copolymer.

In addition, the xylene solubles (Xs) of the propylene-1-butene copolymer exhibit a tacticity of about 3% by weight or less, preferably about 2% by weight or less. The xylene solubles are the content (% by weight) of the copolymer soluble in the cooled xylene determined by dissolving the propylene-1-butene copolymer in xylene and crystallizing the insoluble portion from the cooling solution. The xylene solubles contain polymer chains of low stereoregularity, and the lower the content of the xylene solubles, the higher the stereoregularity.

The propylene-1-butene copolymer produced according to the present invention may have a high melting point (Tm) as well as improving the stereoregularity as described above. For example, the melting point (Tm) of the propylene-1-butene copolymer may be about 130 ° C or higher, or about 130 to about 180 ° C, preferably about 130 to about 150 ° C, Lt; 0 > C.

In addition, the propylene-1-butene copolymer produced according to the present invention may exhibit a crystallization temperature (Tc) of about 80 to about 120 캜, preferably about 85 to about 100 캜.

In addition, the propylene-1-butene copolymer produced according to the present invention exhibits high fluidity. For example, the propylene-1-butene copolymer prepared according to the present invention has a melt index of at least about 10 g / 10 min, such as from about 10 to about 40 g / 10 min, Has a high melt flow rate (MFR) of from about 15 to about 35 g / 10 min.

In the present invention, matters other than those described above can be added or subtracted as required, and therefore, the present invention is not particularly limited thereto.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

< Example  >

< Synthetic example : Metallocene  Synthesis of Compound &gt;

Synthetic example : &Lt; EMI ID = Metallocene  Synthesis of compounds

(3)

Step 1: (6-t- Butoxyhexyl ) Of dichloromethylsilane  Produce

100 mL of a solution of t-butoxyhexyl magnesium chloride (about 0.14 mol, ether) was added dropwise to 100 mL of a trichloromethylsilane solution (about 0.21 mol, hexane) at -100 ° C over 3 hours, And stirred for 3 hours.

After separating the transparent organic layer from the mixed solution, the separated transparent organic layer was vacuum dried to remove excess trichloromethylsilane. Thus, a transparent liquid (6-t-butoxyhexyl) dichloromethylsilane was obtained (yield: 84%).

^{1 H NMR (500 MHz, CDCl} 3, 7.24 ppm): 0.76 (3H, s), 1.11 (2H, t), 1.18 (9H, s), 1.32 ~ 1.55 (8H, m), 3.33 (2H, t)

Step 2: (6-t- Butoxyhexyl ) ( methyl ) - Bis (2-methyl-4-phenylindenyl) silane  Produce

15.4 mL of n-butyllithium solution (2.5 M, hexane solvent) was slowly added dropwise to 77 mL of 2-methyl-4-phenylindene toluene / THF = 10/1 solution (34.9 mmol) The mixture was stirred for 1 hour and then at room temperature for one day. Subsequently, 5 g of the (6-t-butoxyhexyl) dichloromethylsilane prepared previously was slowly added dropwise to the mixed solution at -78 ° C, and the mixture was stirred for about 10 minutes and then at 80 ° C for 1 hour. The organic layer was separated by adding water, purified silica column, and vacuum dried to obtain a sticky yellow oil (racemic: meso = 1: 1) in a yield of 78%.

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): 0.10 (3H, s), 0.98 (2H, t), 1.25 (9H, s), 1.36-1.50 , 2.26 (6H, s), 3.34 (2H, t), 3.81 (2H, s), 6.87 7.53 (4 H, t), 7.61 (4 H, d)

Step 3: Preparation of [(6-t- Butoxyhexylmethylsilane - Dill ) -Bis (2- methyl -4- Phenyl indenyl )] Zirconium Dichloride  Produce

To a solution of the above-prepared (6-t-butoxyhexyl) (methyl) bis (2-methyl-4-phenyl) indenylsilane ether / hexane = 1/1 solution (3.37 mmol) in n-butyl lithium M in hexane) was slowly added dropwise at -78 ° C, stirred at room temperature for about 2 hours, and then vacuum-dried. Then, the salt was washed with hexane, followed by filtration and vacuum drying to obtain a yellow solid. The ligand salt synthesized in a glove box and bis (N, N'-diphenyl-1,3-propanediamido) dichlorozirconium bis (tetrahydrofuran) [Zr (C ₅ H ₆ NCH ₂ CH ₂ CH ₂ NC ₅ H ₆ ) Cl ₂ (C ₄ H ₈ O) ₂ ] was weighed in a Schlenk flask, ether was slowly added dropwise at -78 ° C., And stirred for one day. Thereafter, the red reaction solution was separated by filtration, 4 equivalents of an HCl ether solution (1M) was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for 3 hours. After filtration and vacuum drying, the metallocene compound of orange solid component was obtained in a yield of 85% (racemic: meso = 10: 1).

^{1 H NMR (500 MHz, C} 6 D 6, 7.24 ppm): 1.19 (9H, s), 1.32 (3H, s), 1.48 ~ 1.86 (10H, m), 2.25 (6H, s), 3.37 (2H, d), 7.67 (2H, d), 7.63 (2H, d), 6.95

compare Synthetic example : Metallocene  Synthesis of compounds

[Chemical Formula 4]

Stage 1: Dimethylbis (2-methyl-4-phenylindenyl) silane  Produce

21.8 mL of n-butyllithium solution (2.5 M, hexane solvent) was slowly added dropwise to 77 mL of 2-methyl-4-phenylindene toluene / THF = 10/1 solution (49.5 mmol) at 0 ° C, The mixture was stirred for 1 hour and then at room temperature for one day. Thereafter, 2.98 mL of dichloromethylsilane was slowly added dropwise at 0 DEG C or lower, stirred for about 10 minutes, then heated to 80 DEG C and stirred for 1 hour. The organic layer was separated by adding water, and the silica column was purified and vacuum dried to obtain a sticky yellow oil (yield: racemic: meso = 1: 1).

^{1 H NMR (500 MHz, CDCl} 3, 7.24 ppm): 0.02 (6H, s), 2.37 (6H, s), 4.00 (2H, s), 6.87 (2H, t), 7.38 (2H, t), 7.45 (2H, t), 7.57 (4H, d), 7.65 (4H, t), 7.75

Step 2: Preparation of [dimethylsilanediylbis (2- methyl -4- Phenyl indenyl )] Zirconium Dichloride  Produce

10.9 mL of a n-butyllithium solution (2.5 M in hexane) was slowly added dropwise to 240 mL of a dimethyl bis (2-methyl-4-phenylindenyl) silane ether / hexane = 1/1 solution (12.4 mmol) Respectively. Thereafter, the mixture was stirred at room temperature for one day, filtered and vacuum dried to obtain a pale yellow solid. The ligand salt synthesized in a glove box and bis (N, N'-diphenyl-1,3-propanediamido) dichloro zirconium bis (tetrahydrofuran) were dissolved in a Schlenk flask ), Ether was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for one day. The red solution was separated by filtration, dried in vacuo, and a toluene / ether = 1/2 solution was added to obtain a clear red solution. 1.5-2 equivalent of HCl ether solution (1M) was slowly added dropwise at -78 deg. C, followed by stirring at room temperature for 3 hours. After filtration and vacuum drying, the catalyst of orange solid component was obtained in a yield of 70% (racemic only).

^{1 H NMR (500 MHz, C} 6 D 6, 7.24 ppm): 1.32 (6H, s), 2.24 (6H, s), 6.93 (2H, s), 7.10 (2H, t), 7.32 (2H, t) , 7.36 (2H, d), 7.43 (4H, t), 7.60 (4H, d), 7.64

< Manufacturing example  And Comparative Example : Preparation of Supported Catalyst>

Manufacturing example

After supporting methylaluminoxane on silica, the metallocene compound obtained in the above Synthesis Example was carried, and further boron-based promoter catalyst was supported to prepare a supported catalyst.

More specifically, 3 g of silica L203F was preliminarily weighed in a shrinking flask, and 40 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 DEG C for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. 360 占 퐉 ol of the metallocene compound obtained in Synthesis Example 1 was dissolved in toluene, and the mixture was reacted at 75 占 폚 for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed with toluene. And 252 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate were reacted at 75 ° C for 5 hours. After completion of the reaction, the reaction mixture was washed with toluene, washed again with hexane, and vacuum-dried to obtain 5 g of silica-supported metallocene catalyst in the form of solid particles.

compare Manufacturing example

A supported catalyst was prepared in the same manner as the preparation example except that the metallocene compound obtained in Comparative Synthesis Example was used instead of the metallocene compound obtained in the above Synthesis Example.

< Example  And Comparative Example >

Example  One

(1) Propylene-1- Butene  Preparation of Copolymer

Bulk-slurry polymerization of propylene and 1-butene was carried out using two continuous loop reactors. At this time, triethylaluminum (TEAL) and hydrogen gas were respectively introduced by using a pump, and for the bulk-slurry polymerization, mud catalyst mixed with oil and grease of 20 wt% of the catalyst prepared in the above-mentioned supported catalyst production example was used. The reactor was operated at a temperature of 70 ° C and a production rate of about 40 kg per hour.

The propylene-1-butene copolymer thus prepared was measured for physical properties by the following measurement method, and shown in Tables 2 to 3 in Example 1-1.

(2) Granulation : Process of prescribing and extruding additive

100 kg of the propylene-1-butene copolymer prepared in (1) above was mixed with 500 ppm of a neutralizing agent (Calcium stearate), 500 ppm of a primary antioxidant (Irganox 1010, manufacturer: BASF) : BASF) 1000 ppm, slip agents (Erucamide, Manufacturer: ALDRICH) 1000 ppm, anti-blocking agent (SiO _2, manufacturer: SIPERNAT) by prescribing the additives of 1000 ppm a Strand as at 180 to 220 ℃ 5 to 15kg / h And the strand was pelletized with a pelletizer at approximately 500 to 900 rpm.

In order to improve the transparency of the product, a resin composition was prepared by prescribing and extruding 2500 ppm of Millaid 3988 (manufacturer: Milliken), 2500 ppm of NU700 (manufactured by Dongbu Chemical), and 2500 ppm of NX8000 (manufactured by Milliken). The flexural modulus, impact strength, and haze of the thus-prepared resin composition were measured by the following measurement methods and shown in Table 4 in Example 1-2.

The flexural modulus, impact strength and haze of the resin composition were measured by the following measuring methods except that no nucleating agent was added in the extrusion step, and the results are shown in Table 5 as Comparative Examples 1-3 .

Example  2 to 7

In Example 1, polymerization was carried out in the same manner as in Example 1, except that the amount of 1-butene and the detailed operating conditions were different.

Comparative Example  One

Polymerization was carried out in the same manner as in Example 1 except that 1-butene was not used but polymerization was carried out only with propylene.

Comparative Example  2 to 4

In Example 1, propylene polymerization or bulk-slurry copolymerization of propylene and 1-butene was carried out in the same manner as in Example 1, except that the supported catalyst obtained in Comparative Production Example was used and the detailed process conditions were changed .

The detailed operating conditions of Examples 1 to 6 and Comparative Examples 1 to 4 are summarized in Table 1 below.

Temperature
(° C) pressure
(kg / cm2) Catalyst input
(g / hr) Propylene
input
(kg / hr) 1-butene
input
(wt%) TEAL
input
(ppm) Hydrogen
input
(ppm) Example 1 70 35 1.2 80 1.0 50 100 Example 2 70 35 1.1 80 2.0 50 100 Example 3 70 35 1.1 80 3.0 50 100 Example 4 70 35 1.0 80 4.0 50 100 Example 5 70 35 1.0 80 5.0 50 100 Example 6 70 35 1.0 80 6.0 50 100 Comparative Example 1 70 35 1.2 80 0.0 50 400 Comparative Example 2 70 35 1.5 80 0.0 50 400 Comparative Example 3 70 35 1.5 80 2.0 50 100 Comparative Example 4 70 35 1.4 80 4.0 50 100

&Lt; Measurement method of physical properties of polymer &

(1) Catalytic activity

The ratio of the weight of polymer produced per gram of supported catalyst (g) to the weight of polymer produced per unit time (h) (kgPP) and the weight of polymer generated per umol of metallocene compound content (umol) ).

(2) Melt index

Measured at 230 占 폚 under a load of 2.16 kg according to ASTM D1238, and expressed as the weight (g) of the polymer that has been melted for 10 minutes.

(3) 1-butene content

After fixing the film or film specimen according to ASTM D5576 in a magnetic holder of the FT-IR equipment, the peak of the peak at 4800 ~ 3500cm- ¹ reflecting the specimen thickness in the IR absorption spectrum and the peak at 790 ~ 660cm- ¹ peak Area was measured and calculated. The measured value was substituted into the calibration equation obtained by plotting the value obtained by dividing the area of 790 to 660 cm ^-1 peak of the standard sample by the peak height of 4800 to 3500 cm ^-1 .

(4) Melting point (Tm)

The temperature was increased to 200 DEG C, held at that temperature for 5 minutes, then decreased to 30 DEG C, and the temperature was again increased to set the melting point at the top of the curve of DSC (Differential Scanning Calorimeter, TA). At this time, the temperature rise and fall speed was 10 ° C / min, and the melting point was measured at the second temperature rise.

(5) Density

A sample was prepared with a press mold of 210 占 폚 in a sheet having a thickness of 3 mm and a radius of 2 cm and measured at 10 占 폚 / min on a Mettler scale.

(6) Xylene solubles (Xylene Soluble)

Xylene was added to the sample, and the sample was preheated by heating at 135 ° C for 1 hour and cooling for 30 minutes. 1ml / min from OminiSec (Viscotek FIPA) equipment. When the base line of RI, DP and IP was stabilized by flowing Xylene for 4 hours at the flow rate, the concentration and the injection amount of the pretreated sample were written and the peak area was calculated

(7) Particle size

The samples were injected into a hopper with a light diffraction particle size analyzer (Symatec HELOS), and the method was set in the range of 50 to 3500 μm to confirm APS (Average Particle Size), Span value, and content below 200um (fine powder).

(8) Tensile strength and elongation

The thickness of the film specimen was fixed to the UTM equipment (ZWICK Roell) and the cross-sectional area was recorded. The MD and TD directions of the specimen were measured at a speed of 200 mm / min. The tensile strength (Kg / ㎠) was confirmed by dividing the elongation (%), yield strength (Kgf) and fracture point load (Kg) of each specimen by the cross - sectional area (㎠).

(9) Flexural Strength

After mounting the specimen on the support in accordance with ASTM D790, the strength (Kgf / ㎠) was measured when the load was applied at approximately 30 ~ 50mm / min with loading nose. The bending elastic modulus of stiffness was measured by the initial tilt value according to the bending strength and flexural strength, which are the maximum values at which the loading nose does not increase any more.

(10) Impact Strength

After the specimen with V-Notch was fixed according to ASTM D256A, the strength (J / m) at which the specimen was broken by applying a pendulum was measured.

(11) Haze

The degree (%) of refraction of light when light was shot in 1T (1mm) and 2T (2mm) of the specimen in accordance with ASTM D1003 was measured. Haze can measure the transparency of a specimen at Td (refracted light) / Tt (passed light) x 100 (%).

Propylene-1- Butene  Properties of Copolymer activation
(kg / g-cat.) Melt Index
(g / 10 min) 1-butene content
(wt%) Melting point
(° C) density
(g / cm3) Example 1-1 28.9 19 1.3 146.1 0.9 Example 2-1 29.5 21 2.3 143.0 0.9 Example 3-1 30.1 23 3.7 138.0 0.9 Example 4-1 32.2 27 5.0 134.4 0.9 Example 5-1 31.8 24 6.8 131.8 0.9 Example 6-1 31.7 26 7.7 130.0 0.9 Comparative Example 1-1 25.6 58 0.0 148.9 0.9 Comparative Example 2-1 22.1 68 0.0 149.9 0.9 Comparative Example 3-1 24.8 24 2.1 144.5 0.9 Comparative Example 4-1 25.5 26 4.0 139.1 0.9

Propylene-1- Butene  Properties of Copolymer Xylene soluble fraction (wt%) Particle Size (㎛) Tensile strength (kg / cm 2) Elongation (%) Example 1-1 0.7 928 324 > 500 Example 2-1 0.5 933 316 > 500 Example 3-1 0.5 974 305 > 500 Example 4-1 0.7 988 299 > 500 Example 5-1 0.9 1011 291 > 500 Example 6-1 0.9 1117 286 > 500 Comparative Example 1-1 0.6 898 353 <100 Comparative Example 2-1 0.8 877 341 <100 Comparative Example 3-1 1.2 895 311 > 500 Comparative Example 4-1 1.2 887 286 > 500

Nucleating agent  Formulation Propylene-1- Butene  Physical Properties of Copolymer Resin Composition Flexural modulus Impact strength Haze Kgf / ㎠ Kgfcm / cm 1mm 2mm Examples 1-2 15,286 3.4 3.7 14.2 Example 2-2 14,062 3.4 4.2 13.9 Example 3-2 12,971 3.6 4.3 13.3 Example 4-2 12,889 3.7 4.3 13.1 Example 5-2 12,042 3.9 4.5 12.8 Example 6-2 11,477 3.9 4.5 12.5 Comparative Example 1-2 15,887 3.2 3.6 14.5 Comparative Example 2-2 15,452 3.2 5.7 17.4 Comparative Example 3-2 13,880 3.4 4.8 15.0 Comparative Example 4-2 12,324 3.5 4.1 14.1

Nucleating agent Non-prescription  Propylene-1- Butene  Physical Properties of Copolymer Resin Composition Flexural modulus Impact strength Haze Kgf / ㎠ Kgfcm / cm 1mm 2mm Comparative Examples 1-3 13,124 2.7 53.3 75.2 Comparative Examples 2-3 12,634 3.1 51.1 74.3 Comparative Examples 3-3 11,105 3.3 47.1 74.2 Comparative Example 4-3 10,534 3.4 39.5 70.2 Comparative Examples 5-3 9,976 3.6 35.2 68.4 Comparative Example 6-3 9,348 3.7 34.4 65.1 Comparative Example 1-3 13,807 2.7 54.2 75.8 Comparative Example 2-3 13,775 2.6 56.6 76.8 Comparative Example 3-3 12,458 3.1 52.2 75.5 Comparative Example 4-3 10,930 3.3 50.2 75.0

As shown in Tables 2 and 3, the propylene-1-butene of Examples 1-1 to 6-1 prepared by polymerizing propylene and 1-butene in the presence of the catalyst containing the metallocene compound of the above- The copolymer shows low xylene solubles in comparison with the comparative example, and thus has characteristics of odorless, low elution characteristics and high stereoregularity. In addition, it is expected to be applicable to fibers, particularly long fiber nonwoven fabrics (spun bond) because of excellent tensile strength and flexibility (elongation).

In addition, as shown in Tables 3 and 4, the propylene-1-butene copolymer resin compositions of Examples 1-2 to 6-2 prepared by adding the nucleating agent to the propylene and 1-butene copolymers and extruding the same Can be confirmed to exhibit an excellent flexural modulus and impact strength, while remarkably improving transparency as compared with Comparative Examples 1-3 to 6-3 produced by extrusion without adding a nucleating agent.

Claims (17)

A process for producing propylene and 1-butene in the presence of a metallocene compound represented by the following formula (1), an alkylaluminoxane-based cocatalyst, and a boron-based cocatalyst supported on a carrier in a content ratio of 99.5: 0.5 to 85:15 Polymerizing the propylene-1-butene copolymer to prepare a propylene-1-butene copolymer; And
Adding a nucleating agent to the propylene-1-butene copolymer and extruding the propylene-1-butene copolymer;
[Chemical Formula 1]

In Formula 1,
M ¹ is a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide series transition metal or an ethanide series transition metal;
X is the same or different halogen;
A is a bridge group connecting an indenyl group as an element of Group 14;
R ¹ is alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms;
R ² is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms;
R ³ , R ^{3 '} , R ⁴ and R ^4' are the same or different and each is an alkyl having 1 to 20 carbon atoms, an alkenyl having 2 to 20 carbon atoms, an alkylaryl having 7 to 20 carbon atoms, Arylalkyl or aryl of 6 to 20 carbon atoms;
n is an integer of 1 to 20;
The compound according to claim 1, wherein R ¹ and R ² in the general formula (1) are each alkyl having 1 to 4 carbon atoms; R ³ and R ^{3 '} are each alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; R ⁴ and R ^{4 '} are each aryl having 6 to 20 carbon atoms or alkylaryl having 7 to 20 carbon atoms; n is an integer from 1 to 6; And A is silicon (Si).
The method for producing a propylene-1-butene copolymer resin composition according to claim 1, wherein the nucleating agent comprises a carbon-based compound.
The method for producing a propylene-1-butene copolymer resin composition according to claim 1, wherein the nucleating agent comprises 2000 to 3000 ppm based on the weight of the propylene-1-butene copolymer.
The process for producing a propylene-1-butene copolymer according to claim 1, wherein at the step of adding the nucleating agent to the propylene-1-butene copolymer and extruding the same, at least one selected from the group consisting of neutralizing agents, antioxidants, slip agents, anti-blocking agents, UV stabilizers, A method for producing a propylene-1-butene copolymer resin composition further comprising an additive.
delete The method of producing a propylene-1-butene copolymer resin composition according to claim 1, wherein the alkylaluminoxane-based co-catalyst is at least one selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, and butyl aluminoxane Way.
The method of claim 1, wherein the boron-based promoter is selected from the group consisting of dimethylanilinium tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, (Pentafluorodiphenyl) borate, and a method for producing the propylene-1-butene copolymer resin composition.
The process for producing a propylene-1-butene copolymer according to claim 1, wherein the support is at least one selected from the group consisting of silica, silica-alumina and silica-magnesia.
The propylene-1-butene copolymer resin composition according to claim 1, wherein the polymerization of propylene and 1-butene is carried out by reacting at a temperature of 25 to 500 ° C and a pressure of 1 to 100 kgf / cm ² for 1 to 24 hours &Lt; / RTI &gt;
delete The method of claim 1, wherein the polymerization of the propylene and 1-butene is from 10 to hydrogen of 2000ppm (H ₂₎ a propylene-1-butene method for manufacturing a copolymer resin composition is carried out in the gas.
A propylene-1-butene copolymer resin composition obtained by the production method of claim 1.
14. The propylene-1-butene copolymer resin composition according to claim 13, wherein the propylene-1-butene copolymer is a random copolymer.
14. The propylene-1-butene copolymer resin composition according to claim 13, wherein the haze value measured at intervals of 1 mm is 10% or less based on ASTM D1003 standard, and the haze value measured at 2 mm intervals is 20% or less.
The propylene-1-butene copolymer resin composition according to claim 13, wherein the flexural modulus value measured according to ASTM D790 standard is 10,000 kgf / cm 2 or more.
The propylene-1-butene copolymer resin composition according to claim 13, wherein an IZOD impact strength value measured according to ASTM D256A standard is not less than 2.5 kgfcm / cm.