WO2017159994A1

WO2017159994A1 - Polypropylene

Info

Publication number: WO2017159994A1
Application number: PCT/KR2017/001550
Authority: WO
Inventors: 최지호; 정인용; 노경섭; 이원상; 전상진; 안상은; 이상훈
Original assignee: 주식회사 엘지화학
Priority date: 2016-03-18
Filing date: 2017-02-13
Publication date: 2017-09-21

Abstract

The present invention relates to a polypropylene which exhibits high transparency and has a very low degree of volatile organic compounds generation, which has a total volatile organic compounds (TVOC) value of 60 μg/g or less, which is measured according to VDA277 standardized by the German Automobile Industry Association by heating the polypropylene for 12 to 5 hours and converting all hydrocarbons detected per 1 g into an acetone content, and a haze value of 5% or less.

Description

【Specification】

[Name of invention]

Polypropylene 【Technical Fields】

Cross Citation with Related Application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0032962 of March 18, 2016 and Korean Patent Application No. 10-2017-0018677 of February 10, 2017, All content disclosed in the literature is included as part of this specification.

The present invention relates to polypropylene, which exhibits high transparency and has a very low generation of volatile organic compounds.

[Technique to become background of invention]

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed for their respective characteristics. The Ziegler-Natta catalyst has been widely applied to existing commercial processes since the invention in the 50's, but because it is a multi-site catalyst having many active sites, the molecular weight distribution of the polymer is broad, and the composition of the comonomer There is a problem in that there is a limit in securing the desired physical properties because the distribution is not uniform.

The metallocene catalyst is composed of a combination of a main catalyst composed mainly of a transition metal compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum. Such a catalyst is a homogeneous complex catalyst, which is a single site catalyst. The polymer has a narrow molecular weight distribution and a homogeneous composition distribution of comonomers according to the characteristics of a single active site. It has the property to change.

On the other hand, ansa-metallocene compound is an organometallic compound containing two ligands connected to each other by a bridge group, the bridge The bridge group prevents the rotation of the ligand and determines the activity and structure of the metal center.

Such ansa-metallocene compound is used as a catalyst for the production of olefinic homopolymers or copolymers. In particular, the ansa-metallocene compound containing a cyclopentadienyl-fluorenyl ligand can produce a high molecular weight polyethylene, and it is known that the microstructure of the polypropylene can be controlled. have. In addition, it is known that ansa-metallocene compound containing an indenyl ligand can produce an olefin polymer having excellent activity and improved stereoregularity.

On the other hand, in order to use olefin polymers, especially polypropylene, for cosmetics, food containers, etc., high transparency and low volatile organic compounds are required. In the case of using a conventional Ziegler-Natta catalyst, polypropylene having such characteristics Difficult to manufacture with high productivity and yield.

[Content of invention]

Problem to be solved

Accordingly, the present invention has completed the present invention by using a metallocene catalyst having a specific structure instead of the Ziegler-Natta catalyst, thereby confirming that polypropylene having high transparency and low generation of volatile organic compounds can be produced. [Measures of problem]

The present invention is measured according to VDA277 standardized by the German Automobile Industry Association, and the value of total volatile organic compounds (TVOC), which is the value of hydrocarbons detected per gram of acetone by heating at 120 ^° C. for 5 hours, is 60 less than iiglg

Haze provides polypropylene with 5% or less.

Hereinafter, a polypropylene according to a specific embodiment of the present invention will be described in more detail. As used herein, the term 'polypropylene', which is prepared by polymerizing propylene, means a propylene homopolymer or a propylene / ethylene copolymer. In addition, the 'polypropylene' prepared in the present invention is polymerized under a metallocene catalyst to be described later, and has a characteristic that the molecular weight distribution (Mw / Mn) is 3.5 or less, or L5 to 3.5, or 1.5 to 3.5. In general, polypropylene made with a Ziegler-Natta catalyst has a wide molecular weight distribution, and thus can be distinguished from polypropylene made with a Ziegler-Natta catalyst by the molecular weight distribution.

The polypropylene of one embodiment may exhibit very low volatile organic compound emissions.

The amount of volatile organic compound released is measured to confirm the content of the volatile organic compound released under certain conditions (temperature and time, etc.), and can be measured according to VDA277 and VDA278 standardized by the German Automobile Industry Association. In the present specification, 'the amount of volatile organic compounds emissions' means the sum of the TVOC value measured according to VDA277 and the VOC and FOG value measured according to VDA278.

In more detail, the volatile organic compound emission amount may be divided into total volatile organic compounds (TVOC) and volatile organic compounds / fogging (VOC / FOG).

TVOC (total volatile organic compounds) is measured according to VDA277, standardized by the German Automobile Industry Association, and it means the value of acetone in terms of all hydrocarbons detected per gram by heating at 120 ^° C for 5 hours.

VOC (volatile organic compounds) is measured according to VDA278, standardized by the German Automobile Industry Association, and is converted to the content of toluene of 1 to 25 carbon straight chain hydrocarbons detected per gram by heating at 90 ^° C for 30 minutes. FOG (fogging) is measured according to VDA278 standardized by the German Automobile Industry Association, which is heated at 120 ^° C for 1 hour to convert 14 to 32 carbon atoms detected per gram into the content of nucleodecane. It means the value. Polypropylene produced using the existing Ziegler-Natta catalyst has a high emission of volatile organic compounds, making it difficult to be applied to automobile interior materials or home appliances. However, the polypropylene according to the embodiment of the present invention significantly reduces the amount of volatile organic compound emission, and exhibits a very low amount of volatile organic compound emission at high temperature, which significantly reduces the harmfulness to the human body, and thus is useful for automobile interior materials or home appliances. Can be used.

More specifically, the polypropylene according to the embodiment has a TVOC value of 60 g / g or less, which is a value obtained by converting all hydrocarbons detected per 1 g into acetone content by heating at 120 ^° C. for 5 hours according to VDA277. 50 // g / g or less, or 40 zg / g or less, or 35 g / g or less. The lower the TVOC value is, the lower the lower limit may be 0 / / g or more, or 1 i lg or more, or 10 g / g or more.

The TVOC value according to VDA277 may be measured using a headspace-GC (gas chromatography) -FID (flame-ionization detector). In addition, the polypropylene according to the embodiment is a value of VOC (volatile organic compounds), which is a value obtained by converting a linear hydrocarbon having 1 to 25 carbon atoms detected per 1 g of toluene by heating at 90 ^° C. for 30 minutes according to VDA278. It may be up to 30 ig / g, or up to 25 / g / g, or up to 20 / g / g. The lower the VOC value is, the more advantageous it is, so the lower limit may be preferably 0 lg or more, or 1 / g / g or more, or 10 / g / g or more.

In addition, the polypropylene according to the embodiment has a FOG (fogging) value, which is a value obtained by converting a linear hydrocarbon having 14 to 32 carbon atoms detected per gram by the content of hexadecane, by heating at 120 ^° C. for 1 hour according to VDA278. 40 / g / g or less, or 35 / ^ g / g or less, or 30 / zg / g or less, or IS! Iglg or less. The lower the FOG value is, the more advantageous it is, so the lower limit may be preferably 0 ig / g or more, or 1 g / g or more, or 10 gig or more.

The VOC and FOG values according to VDA278 may be immediately determined using purge & trap-GC (mass chromatography) -MSD (mass selective detector).

Polypropylene according to an embodiment of the present invention is the volatile organic The amount of compound released, ie, the sum total of TVOC, VOC, and FOG, may be 500 g / g or less, or 300 g / g or less, or 200 / g / g or less, or 100 zg / g or less. The lower the volatile organic compound emission amount is, the more advantageous it is, so the lower limit may be preferably 0 / g or more, or 10 / g / g or more, or 50 iig / g or more.

The polypropylene of the embodiment is prepared in the presence of a common supported catalyst comprising two metallocene compounds containing a specific transition metal, as described below, compared to a polymer prepared using a conventional Ziegler-Natta catalyst Since it has a significantly low volatile organic compound emission amount, it is advantageous to apply to products such as injection containers or beverage cups that can be in direct contact with the human body. In addition, the polypropylene of the embodiment has a haze of 5% or less, preferably 4.8% or less. Thus, polypropylene having a low Haze value is excellent in transparency and is applied to injection products such as cosmetics and food containers. This is easy.

In addition, the polypropylene may have a flexural strength (measured according to ASTM D790) of 400 kgf / cin ² or more, preferably 410 kgf / crf to 600 kgf / crf, more preferably 420 to 500 kgf / crf.

Further, the polypropylene may have a melting point (Tm) of 130 ^° C. to 145 ^° C., preferably 140 to 145 ^° C., and a flexural modulus (measured according to ASTM D790) of 14,000 kgf / cin ² or more, preferably May be at least 14,500 kgf / crf, more preferably 15,000 kgf / cin ² to 20,000 kgf / cuf. That is, in spite of such a low melting point, the polypropylene has a high flexural modulus of 14,000 kg ^ cin ² or more, which has the advantage of saving energy in polypropylene processing.

In addition, the polypropylene of the embodiment may have a MFR (measured at 2.16 kg load at 230 ^° C. according to ASTM D1238) of 10 to 25 g / 10min. In order to prepare a polypropylene having an MFR value in the above range, when using a Ziegler-Natta catalyst, a high content of hydrogen should be added in the polymerization step, but as described below, two kinds of metals containing a specific transition metal are used. In the case of using a common supported catalyst containing a high-density compound, relatively low content of hydrogen can be added, so that activity control is easy and process stability is low. There is a growing advantage.

In addition, the polypropylene may have a tensile strength (measured according to ASTM D790) of 300 to 400 kg cuf.

In addition, the polypropylene of the additive embodiment may have a weight average molecular weight of 100,000 to 500,000 g / mol, preferably 100,000 to 200,000 g / mol. Meanwhile, the polypropylene of one embodiment may be prepared by polymerizing propylene in the presence of a common supported catalyst comprising a compound represented by the following Chemical Formula 1, a compound represented by the following Chemical Formula 2, and a carrier:

In Chemical Formula 1,

X is the same or different halogen from each other,

^ Is C _{6 20} aryl substituted with .20 alkyl,

R ₂ , R ₃ and R 4 are each independently hydrogen, halogen, C ^ o alkyl, C: alkenyl

C _1-20 alkylsilyl, 20 silylalkyl, C _1-20 alkoxysilyl, C _1-20 ether, C _1-20 silylether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C ₇ - ₂₀ arylalkyl and,

A is carbon, silicon or germanium,

R ₅ is C o alkyl substituted with alkoxy,

R ₆ is hydrogen, C o alkyl or C _2-20 alkenyl,

[Formula ² ]

In Chemical Formula 2,

X 'is the same or different halogen from each other,

^ Is C _6-20 aryl substituted with C o alkyl,

R ' ₂ , R'3 and R'4 are each independently hydrogen, halogen, C _1-20 alkyl, C ₂ ᅳ 20 alkenyl, C _1-20 alkylsilyl, C o silylalkyl, C _1-20 alkoxysilyl , C _1-20 ether, C _1-20 silylether, C _1-20 alkoxy, C ₆ ᅵ 20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,

A 'is carbon, silicon or germanium,

R ' ₅ is d_ ₂₀ alkyl substituted with C alkoxy,

R ' ₆ is hydrogen, alkyl or C ₂ ¨ ₂₀ alkenyl.

In the common supported catalyst, the molar ratio of the compound represented by Formula 1 and the compound represented by Formula 2 is 2: 1 to 1: 5. It may be advantageous in terms of maintaining the activity and economical efficiency of the catalyst by showing the optimum catalytic activity and physical properties in the molar ratio.

In Formula 1, preferably, is phenyl substituted with tert-butyl. More preferably, the _ ^ ₄ is tert-butyl-phenyl eu

Also preferably, R ₂ , R ₃ and R 4 are hydrogen.

Also preferably, A is silicon.

Also preferably, R ₅ is 6-tert-subspecific-nucleus and R ₆ is methyl.

Representative examples of the compound represented by Formula 1 are as follows:

In addition, the compound represented by Chemical Formula 1 may be prepared as in Scheme 1 below:

Step 1 is a step of preparing the compound represented by Chemical Formula 1-4 by reacting the compound represented by Chemical Formula 1-2 with the compound represented by Chemical Formula 1-3. It is preferable to use alkyllithium (eg, n-butyllithium) in the reaction, and the reaction temperature is -200 to 0 ° C, more preferably -150 to 0 ^° C. As the solvent, toluene, THF and the like can be used. At this time, after the organic layer is separated from the product, the step of vacuum drying the separated organic layer and removing excess reactant may be further performed. Step 2 is a step of preparing the compound represented by Chemical Formula 1 by reacting the compound represented by Chemical Formula 1-4 with the compound represented by Chemical Formula 1-5. It is preferable to use alkyllithium (eg, n-butyllithium) for the reaction, and the reaction temperature is -200 to 0 ^° C., more preferably -150 to 0 ^° C. Ether, nucleic acid, etc. can be used as a solvent. In addition, in Formula 2, preferably, ^ is phenyl substituted with tert-butyl. More preferably, silver is 4-tert-butyl-phenyl.

Also preferably, R ' ₂ , R' ₃ and R ' ₄ are hydrogen.

Also preferably, A 'is silicon.

Also preferably, R'5 is 6-tert-butoxy-nuclear and R ' ₆ is methyl. Representative examples of the compound represented by Formula 2 are as follows:

In addition, the compound represented by Formula 2 is represented by the following scheme

Can be manufactured:

2-4 The step 1 is to prepare a compound represented by the formula 2-4 by reacting the compound represented by the formula 2-2 with the compound represented by the formula 2-3. It is preferable to use alkyllithium (for example, η-butyllithium) for the reaction, and the reaction temperature is -200 to 0 ^° C., more preferably -150 to 0 ^° C. As the solvent, toluene, THF and the like can be used. At this time, after separating the organic layer from the product, the step of drying the separated organic layer in vacuo and removing excess reaction water may be further performed.

In step 2, the compound represented by Chemical Formula 2-4 is reacted with the compound represented by Chemical Formula 2-5 to form a compound represented by Chemical Formula 2 Manufacturing step. It is preferable to use alkyllithium (eg, n-butyllithium) in the reaction, and the reaction temperature is -200 to 0 ° C, more preferably -150 to 0 ° C. Ether, nucleic acid, etc. can be used as a solvent. On the other hand, in the formula 1 and 2, preferably X and X ', R! And R 'R ₂ and R'2, R ₃ and R'3, RA and R'4, A and A', R ₅ and R ' ₅ , and R ₆ and R' ₆ are the same as each other. That is, it is preferable that only the metal atoms in the compound represented by Formula 1 and the compound represented by Formula 2 have different structures. In the common supported catalyst of the embodiment, the carrier may be a carrier containing a hydroxy group on the surface, and preferably has a semi-reactive hydroxyl group and a siloxane group which are dried to remove moisture on the surface. Carriers may be used. For example, silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, and these are usually oxides, carbonates, such as Na ₂ O, K ₂ C0 ₃ , BaS0 ₄ , and Mg (N0 ₃ ) ₂ , Sulfate, and nitrate components.

The drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, most preferably 300 to 400 ° C. When the drying temperature of the carrier is less than 200 ° C, the moisture is too much and the surface of the carrier reacts with the promoter, and if it exceeds 800 ° C, the surface area decreases as the pores on the surface of the carrier are combined, and the surface is hydroxy on the surface. It is not preferable because there is a lot of groups and only siloxane groups are left to decrease the reaction space with the promoter.

The amount of hydroxyl groups on the surface of the carrier is preferably 1 to 10 mmol / g, more preferably 0.5 to 5 mmol / g. The amount of hydroxy groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or by drying conditions, such as silver _: time, vacuum or spray drying.

If the amount of the hydroxy group is less than 0.1 mmol / g, there is little reaction space with the cocatalyst. If the amount of the hydroxy group is more than 10 mmol / g, it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. not. In the common supported catalyst, the mass ratio of the catalyst (compound represented by the formula (1) and the compound represented by the formula (2)) to the carrier is preferably 1: 1 to 1: 1000. When including the carrier and the catalyst in the mass ratio, it may be advantageous in terms of maintaining the activity and economical efficiency of the catalyst by showing the appropriate supported catalyst activity. In addition, the common supported catalyst may further include a promoter in addition to the compound represented by Formula 1, the compound represented by Formula 2, and a carrier. The promoter may further include one or more of the promoter compounds represented by the following Formula 3, Formula 4 or Formula 5.

[Formula 3]

-[A1 (R ₃₀ ) -O] _m -in Formula 3,

R ₃₀ may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

m is an integer of 2 or more;

[Formula ⁴ ]

J (R3l) 3

In Chemical Formula 4,

R ₃₁ is as defined in Formula 3 above;

J is aluminum or boron;

[Formula ⁵ ]

[EH] ⁺ [ZA ₄ ] ^" or [E] ⁺ [ZA4] In Chemical Formula 5,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a Group 13 element;

A may be the same or different from each other, and each independently 1 or more The hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy.

Examples of the compound represented by Formula 3 include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like, and more preferred compound is methyl aluminoxane.

Examples of the compound represented by Formula 4 include trimethylaluminum triethylaluminum, triisobutylaluminum, tripropylaluminum tributylaluminum, dimethylchloroaluminum, triisopropylaluminum tri-S-butylaluminum, tricyclopentylaluminum, and tripentyl Aluminum triisopentylaluminum, trinuclear silaluminum, trioxalyl aluminum ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum tri-P-allyl aluminum, dimethylaluminum mesoxide, dimethylaluminum trimethylboron, triethyl boron, Triisobutyl boron, tripropyl boron tributyl boron and the like, and more preferred compounds are selected from trimethylaluminum triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra (P-lryl) Boron,

Trimethylammonium tetra (ο, ρ-dimethylphenyl) boron,

Tributylammonium tetra (Ρ-trifluoromethylphenyl) boron ，

Trimethylammonium tetra (Ρ-trifluoromethylphenyl) boron,

Tributylammonium tetrapentafluorophenylboron,

Ν, Ν-diethylanilinium tetraphenylboron,

Ν, Ν-diethylanilinium tetrapentafluorophenylborone ，

Diethyl ammonium tetrapentafluorophenyl boron, triphenyl phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tri Propyl ammonium tetraphenyl aluminum, Trimethylammonium tetra (p-lryl) aluminum,

Tripropylammonium tetra (P-lryl) aluminum,

Triethylammonium tetra (ο, ρ-dimethylphenyl) aluminum ，

Tributylammonium tetra (Ρ-trifluoromethylphenyl) aluminum,

Trimethylammonium tetra (Ρ-trifluoromethylphenyl) aluminum,

Tributylammonium tetrapentafluorophenylaluminum,

Ν, Ν-diethylanilinium tetraphenylaluminum,

Ν, Ν-diethylanilinium tetrapentafluorophenylaluminum,

Diethylammonium tetrapenta tetraphenyl aluminum,

Triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra (Ρ-lryl) boron,

Triethylammonium tetra (ο, ρ-dimethylphenyl) boron,

Tributylammonium tetra (Ρ-trifluoromethylphenyl) boron ，

Triphenylcarbonium tetra (Ρ-trifluoromethylphenyl) boron,

Triphenylcarbonium tetrapentafluorophenylboron, and the like. The common supported catalyst may be prepared by supporting a cocatalyst compound on a carrier, supporting the compound represented by Formula 1 on the carrier, and supporting the compound represented by Formula 2 on the carrier. The order of loading can be changed as needed.

In the preparation of the common supported catalyst, a hydrocarbon solvent such as pentane, nucleic acid, heptane, or the like, or an aromatic solvent such as benzene, toluene, or the like may be used. The metallocene compound and the cocatalyst compound can also be used in the form of silica or alumina. In addition, the polypropylene of the above embodiment may be prepared by polymerizing propylene in the presence of the above-described common supported catalyst.

In the method for producing the polypropylene, in addition to the propylene, ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1-octene, 1-decene, 1-undecene , 1-dodecene, 1-tetradecene, 1-hex-decene, it may be used to add the 1-ahyito _metallocene: You may mix and copolymerize 2 or more types of these. Preferably, the polypropylene according to the invention is a propylene homopolymer, a random copolymer of propylene and ethylene, or a terpolymer of ethylene, propylene and C _4-8 olefins (particularly 1-butene).

The polymerization reaction can be _{carried out} by homopolymerization or copolymerization of two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.

The common supported catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, nucleic acid, heptane, nonane, decane, and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, chlorine such as dichloromethane and chlorobenzene. The solution may be dissolved or diluted in a hydrocarbon solvent substituted with an atom or the like. The solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkyl aluminum, and may be carried out by further using a promoter.

Here, the polymerization may be carried out by reacting for 1 to 24 hours at a temperature of 25 to 500 ^° C and a pressure of 1 to 100 kgf / cuf. At this time, the polymerization reaction temperature is preferably 25 to 200 ^° C., more preferably 50 to 100 ^° C. Further, the polymerization reaction pressure is preferably 1 to 70 kgf / cirf, more preferably 5 to 40 kgf / crf. The polymerization reaction time is preferably 1 to 5 hours.

The polymerization process may control the molecular weight range of the polypropylene finally produced according to hydrogenation or no addition conditions. In particular, under the condition that no hydrogen is added, high molecular weight polypropylene can be produced. When hydrogen is added, low molecular weight polypropylene can be produced even with a small amount of hydrogen. At this time, the hydrogen content added to the polymerization process is in the range of 07 L to 4 L at 1 atmosphere of semi-aqueous conditions, or is supplied at a pressure of 1 bar to 40 bar or 168 ppm to 8,000 in the range of molar hydrogen content relative to olefinic monomers. It can be supplied in ppm. 【Effects of the Invention】

Since the polypropylene according to the present invention exhibits high transparency and a very low generation of volatile organic compounds, it can be used in products such as injection containers or beverage cups that can be in direct contact with the human body.

[Specific contents to carry out invention]

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

Step 1)

Preparation of (6-t-Buroxynucleosil) (methyl) -bis (2-methyl-4-tert-butyl-phenylindenyl) silane 2-methyl-4-tert-butylphenylindene (20.0 g, 76 mmol ) Was dissolved in toluene / THF = 10/1 solution (230 mL), and then n-butyllithium solution (2.5 M, nucleic acid solvent, 22 g) was slowly added dropwise at 0 ^° C, followed by stirring at room temperature for one day. It was. Thereafter, (6-t-butoxynucleosil) dichloromethylsilane (1.27 g) was slowly added dropwise to the mixed solution at -78 ^° C, and stirred for about 10 minutes, followed by stirring at room temperature for 1 day. Thereafter, water was added to separate the organic layer, and the solvent was distilled under reduced pressure to obtain ₍₆₄ -subspecific nuclear chamber _{) (} methyl) -bis ₍ 2_methyl_4-tert-butyl-phenylindenyl) silane.

1 H NMR (500 MHz, CDC1 ₃ , 7.26 ppm): -0.20-0.03 (3H, m), 1.26 (9H, s), 0.50-1.20 (4H, m), 1.20-1.31 (11H, m), 1.40- 1.62 (20H, m), 2.19-2.23 (6H, m), 3.30-3.34 (2H, m), 3.73-3.83 (2H, m), 6.89-6.91 (2H, m), 7.19-7.61 (14H, m Step 2) Preparation of [(6-t-subspecific nucleosilmethylsilane-diyl) -bis (2-methyl-4-tert-butylphenylindenyl)] zirconium dichloride

Prepared in step 1

(6-subspecific nuclear chamber) (methyl) -bis (2-methyl-4-tert-butyl-phenylindenyl) silane

After dissolving in toluene / THF = 5/1 solution (95 mL), n-butyllithium solution (2.5 M, nucleic acid solvent, 22 g) was slowly added dropwise at -78 ^° C, followed by stirring at room temperature for one day. . Bis (Ν, Ν'-diphenyl-1,3-propanediazido) dichlorozirconium bis (tetrahydrofuran) [Zr (C ₅ H ₆ NCH ₂ CH ₂ NC ₅ H ₆ ) Cl ₂ (C ₄ H ₈ 0) ₂ ] was dissolved in toluene (229 mL), then slowly added dropwise at -78 ^° C and stirred for 1 day at room temperature. The reaction solution was stirred at -78 ^° C, and then HC1 ether solution (1 M, 183 mL) was slowly added dropwise and then stirred at 0 ^° C. for 1 hour. After filtration and drying in vacuo, hexane was added and stirred to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure

[(6-t-Buroxynucleosilmethylsilane-diyl) -bis (2-methyl-4-tert-butylphenylindenyl)] zirconium dichloride (20.5 g, 61% in total) was obtained. '

1 H NMR (500 MHz, CDC1 ₃ , 7.26 ppm): 1.20 (9H, s), 1.27 (3H, s), 1.34 (18H, s), 1.20-1.90 (10H, m), 2.25 (3H, s), 2.26 (3H, s), 3.38 (2H, t), 7.00 (2H, s), 7.09-7.13 (2H, m), 7.38 (2H, d), 7.45 (4H, d), 7.58 (4H, d) , 7.59 (2H, d), 7.65 (2H, d)

Step 1)

Preparation of (6-t-Buroxynucleosil) (methyl) -bis (2-methyl-4- (4-t-butylphenyl) indenyl)) silane 2-L in a 3L schlenk flask 150 g of methyl-4- (4-t-butylphenyl) -indene was added, and a solution of toluene / THF (10: 1, 1.73 L) was added and dissolved at room temperature. After cooling the solution to -20 ^° C n-butyllithium solution (n-BuLi, 2.5 M in hexane) 240 mL was slowly added dropwise and stirred at room temperature for 3 hours. Thereafter, the reaction mixture was cooled to -20 ^° C, and then 82 g of (6-t-subsidiary nucleus) dichloromethylsilane and 512 mg of CuCN were slowly added dropwise. The reaction solution was warmed to room temperature, stirred for 12 hours, and 500 mL of water was added. After that, the organic layer was separated, dehydrated with MgSO ₄ and filtered. The filtrate was distilled under reduced pressure to give a yellow oil.

NMR (500 MHz, CDC1 ₃ , 7.26 ppm): -0.09--0.05 (3H, m), 0.40-0.60 (2H, m), 0.80-1.51 (26H, m), 2.12-2.36 (6H, m) , 3.20-3.28 (2H, m), 3.67-3.76 (2H, m), 6.81-6.83 (2H, m), 7.10-7.51 (14H, m) step 2) rac-[(6-t-buroxynucleus Preparation of Methylsilanediyl) -bis (2-methyl-4- (4-t-butylphenyl) indenyl)] hafnium dichloride

Into a 3 L schlenk flask was added (6-t- butyloxysil) (methyl) bis (2-methyl-4- (4-t-butylphenyl)) indenylsilane, prepared previously, 1 L of ethyl ether was added and dissolved at room temperature. After cooling the solution to -20 ^° C, 240 mL of n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise and stirred at room temperature for 3 hours. After that, the reaction solution was quenched to -78 ^° C, and 92 g of hafnium chloride was added thereto. The reaction solution was raised to room temperature, stirred for 12 hours, and the solvent was removed under reduced pressure. 1 L of dichloromethane was added and the insoluble inorganic salts were filtered off. The filtrate was dried under reduced pressure, and 300 mL of dichloromethane was added again to precipitate crystals. The precipitated crystals were filtered and dried to give 80 g of rac-[(6-t-subspecific nucleosilsilylsilanediyl) -bis (2-methyl-4- (4-t-butylphenyl) indenyl)] hafnium dichloride (Rac: meso = 50: 1).

1 H NMR (500 MHz, CDC1 ₃ , 7.26 ppm): 1.19-1.78 (37H, m), 2.33 (3H, s), 2.34 (3H, s), 3.37 (2H, t), 6.91 (2H, s), 7.05-7.71 (14H, m) Preparation Example 3 Preparation of Supported Catalysts

3 g of silica L203F was pre-weighed in a shrink flask Methyl aluminoxane (MAO) 10 mtn was added and reacted at 95 ^° C for 24 hours. After precipitation, the upper layer was removed and washed once with toluene. 60 μπιοΐ compound prepared in Preparation Example 2 was dissolved in toluene, and reacted at 75 ^° C. for 5 hours. After the completion of the reaction, when the precipitation was completed, the supernatant solution was removed and the remaining reaction product was washed once with toluene. Subsequently, 20 μιη of the compound prepared in Preparation Example 1 was dissolved in toluene, and further reacted at 75 ^° C. for 2 hours. After the reaction was completed, the precipitate was finished, the supernatant solution was removed, and the remaining reaction product was washed once with toluene. 64 μηι of dimethylanilinium tetrakis (pentafluorophenyl) borate was added and reacted at 75 ^° C. for 5 hours. After the reaction was completed, washed with toluene, washed again with nucleic acid, and dried under vacuum to obtain a silica supported metallocene catalyst in the form of solid particles. Example 1

A 2 L stainless reaction vessel was dried in vacuo at 65 ^° C., then cooled, and 1.5 mmol of triethylaluminum, 337 ppm hydrogen, and 770 g of propylene were added at room temperature. After stirring for 10 minutes, 0.004 g of the supported catalyst prepared in Preparation Example 3 was dissolved in 20 mL of TMA-prescribed nucleic acid and introduced into a reaction vessel under nitrogen pressure. The reaction mixture was then slowly warmed up to 7 rc and polymerized for 1 hour. After completion of the reaction, unreacted propylene was vented. Example 2

In the same manner as in Example 1, except that the amount of hydrogen was changed to 200 ppm in Example 1 was polymerized the olefin resin. Comparative Example 1

The 2 L stainless reaction vessel was vacuum dried at 65 ^° C. and then cooled, and 1.5 mmol of triethylaluminum, 500 ppm hydrogen, and 770 g of propylene were added at room temperature. After stirring for 10 minutes, 0.01 g of a Ziegler-Natta catalyst was dissolved in 20 mL of TMA-prescribed nucleic acid and added to the reactor under nitrogen pressure. After the reaction temperature was slowly raised to 70 ^° C. and then polymerized for 1 hour. After the reaction Uncoated propylene was vented. Comparative Example 2

An olefin monomer was polymerized in the same manner as in Comparative Example 1 except that the charge amount of hydrogen was changed to 725 ppm in Comparative Example 1. Experimental Example

The following physical properties were measured with the polypropylene of the said Example and the comparative example.

1) Mn, Mw, and MWD: Melt the sample in l, 2,4-Trichlorobenzene containing 0.0125% of BHT using PL-SP260 for 10 hours at 160 ^° C for 10 hours, and measure temperature 160 using PL-GPC220. the average molecular weight, weight average molecular weight be in ^° C was measured. The molecular weight distribution was expressed as the ratio of weight average molecular weight and number average molecular weight.

2) Melt Index (MFR, 2.16 kg): measured at 2.16 kg load at 230 ^° C according to ASTM D1238, expressed as weight (g) of polymer melted for 10 minutes.

3) Melting point (Tm): The melting point of polypropylene was measured using a differential scanning calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 220 ^° C and maintained at that temperature for 5 minutes, and then lowered to 20 ^° C and increased again. At this time, the rate of rise and fall of the temperature was 10 ^° C / min, respectively. Adjusted.

4) Tensile Strength: Tensile strength was measured according to ASTM D790.

5) Flexural modulus and flexural strength: Flexural modulus and flexural strength were measured according to ASTM D790.

6) Impact strength: After fixing the specimen with V-Notch in accordance with ASTM D256, the strength required when the specimen was broken by pendulum was measured at 23 ^° C.

7) Haze: lights lT (lmm) and 2T (2mm) of the specimen according to ASTM D1003. The degree of refraction (%) of the light at the time of shooting was measured. Haze values can be measured as Td (reflected light) / Tt (passed light) * 100 and the transparency of the specimen can be evaluated.

8) Volatile Organic Compound Emissions: Total volatile organic compounds (TVOC) and volatile organic compounds / fogging (VOC / FOG) dosages were measured under the following conditions.

(1) VDA277

The headspace-GC-FID was used to heat the olefin polymer at 120 ^° C. for 5 hours according to VDA277, standardized by the German Automobile Industry Association, and all hydrocarbons detected per gram of sample were converted to the acetone content G « _g ).

Specifically, after limiting the blank value of the total peak area of the hydrocarbon detected in the empty headspace vessel from the total peak area of the hydrocarbon detected from the sample as shown in Equation 1 below. Divided by the constant (k (G)) obtained from acetone calibration. Then, the obtained value is multiplied by the standard amount of acetone used (acetone 2 per 1g of sample) and the weight ratio of carbon to total weight of acetone (e) 6204 to calculate the acetone content (EG) in terms of hydrocarbons detected per 1g of sample. Obtained.

The converted value is defined as a TVOC value and shown in Table 2. [Equation 1]

p ₌ four peak areas-Blank value _{χ χ Q}

ϋ— k (G). '^'

(2) VDA278

Purge & trap-GC-MSD was used to heat the olefin polymer at 90 ^° C for 30 minutes in accordance with VDA278 standardized by the German Automobile Industry Association, and the amount of toluene (up to n-C25) /). The converted value is defined as a VOC value and is shown in Table 2.

On the other hand, according to the standardized in German Automobile Industry Association VDA278 using a purge & trap-GC-MSD, and heating the olefin polymer for 1 hour at 120 ^° C Hydrocarbons (n-C14 to n-C32) detected per gram of sample were converted to the content of nucledecane (/ zg). This converted value is defined as the FOG value and shown in Table 2. Specifically, as shown in Equation 2, the total peak area of the hydrocarbon detected from the sample is divided by the content of the sample using the integrated peak area, and in the case of VOC, the Rf (response factor) constant value of toluene is multiplied and In the case of multiplying the Rf constant value of nucleodecane, the hydrocarbon detected per 1 g of the sample was converted into toluene or nucleodecane content (/ g).

[Equation 2]

Peak area

Emission = Rf (tolyeoc or cxadeciuie) X ~ ―

1000 X Test portion sample The measurement results are shown in Tables 1 and 2 below.

Table 1 1

[Table 2]

As shown in Table 1 and Table 2, containing a specific transition metal

Prepared in the presence of a common supported catalyst comprising two metallocene compounds Compared to the polypropylene of the comparative example prepared in the presence of a Ziegler-Natta catalyst, the polypropylene of the example has excellent elasticity and mechanical properties such as flexural strength, and has a very low amount of volatile organic compound emission. It is advantageous to apply to products such as injection containers or beverage cups that can be in direct contact.

Claims

【Claims】

【Claim 1】

Measured according to VDA277 standardized by the German Automobile Industry Association, the TVOC (total volatile organic compounds) value, which is a value calculated by converting all hydrocarbons detected per 1 g to the content of acetone by heating at 120 ^° C for 5 hours, is 60 ig/ g or less,

Polypropylene with a haze of 5% or less.

【Claim 2】

According to clause 1,

Measured in accordance with VDA278 standardized by the German Automobile Industry Association, the VOC (volatile organic compounds) value is a value obtained by converting straight-chain hydrocarbons with 1 to 25 carbon atoms detected per gram by heating at 90 ^° C for 30 minutes into the content of toluene. Polypropylene below 30/ _g /g.

【Claim 3】

In clause 1 or clause 2,

Measured according to VDA278 standardized by the German Automobile Industry Association, the FOG (fogging) value is a value obtained by converting straight chain hydrocarbons with 14 to 32 carbon atoms detected per 1 g into the content of hexadecane by heating at 120 ^° C for 1 hour. Polypropylene, not more than 40//g/g.

【Claim 4】

In clause U,

Polypropylene, with a flexural strength (measured according to ASTM D790) of 400 kgf/crf or greater.

【Claim 5】

In paragraph 11,

has a melting point (Tm) of 130 ^° C to 145 ^° C, Polypropylene, having a flexural modulus (measured according to ASTM D790) of 14,000 kg^cin ² or more.

【Claim 6】

According to clause 1,

Polypropylene, with a molecular weight distribution (Mw/Mn) of 3.5 or less.

【Claim 7】

According to clause 1,

Polypropylene with an MFR (measured with a 2.16 kg load at 230 ^° C according to ASTM D1238) of 10 to 25 g/10min.

【Claim 8】

According to clause 1,

A polypropylene having a tensile strength (measured according to ASTM D790) of 300 to 400 kgf/oif.

【Claim 9】

In clause 11,

The polypropylene is a compound represented by the following formula 1, the following formula

Polypropylene, characterized in that it is produced by polymerizing propylene in the presence of a common supported catalyst comprising the compound represented by 2 and a carrier:

[Formula 1]

In the above formula i,

X is the same or different halogen,

^ is C _6-20 aryl substituted with C _1-20 alkyl,

R ₂ , R ₃ and R 4 are each independently hydrogen, halogen, C _1-20 alkyl, C _{2 20} alkenyl,

C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-¾) alkoxysilyl, C _1-20 ether, C _1-20 silylether, C _1-20 alkoxy, C _6-20 aryl, C _{7- 20} alkylaryl, or C _7-20 arylalkyl,

A is carbon, silicon or germanium,

R ₅ is C ₂₀ alkyl substituted with C _1-20 alkoxy,

R ₆ is hydrogen, ₂₀ alkyl, or C ₂ 20 alkenyl,

In Formula 2 above, X' is the same or different halogen,

！ is C _6-20 aryl substituted with C _1-20 alkyl,

R ^* ₂ , R'3 and R'4 are each independently hydrogen, halogen, ₂₀ alkyl, C _{2 20} alkenyl,

C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _1-20 ether, C _1-20 silyl ether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 Alkylaryl, or C 20 arylalkyl,

A' is carbon, silicon or germanium,

R'5 is C _1-20 alkyl substituted with C _1-20 alkoxy,

R'6 is hydrogen, C _1-20 alkyl, or C _2-20 alkenyl. 【Claim 10】

In paragraph 19,

The common supported catalyst further includes one or more of the compounds represented by the following formula (3), the compound represented by the formula (4), and the compound represented by the formula (5), polypropylene:

[Formula 3]

-[A1(R ₃₀ )-O] _m - In Formula 3,

R ₃₀ may be the same or different from each other, and each independently represents halogen; Hydrocarbons having 1 to 20 carbon atoms; or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

m is an integer greater than or equal to 2;

[Formula ⁴ ]

J(R ₃ l)3

In Formula 4 above,

R ₃₁ is as defined in Formula 3 above;

J is aluminum or boron;

[Formula ⁵ ]

[EH] ⁺ [ZA ₄ ] ^" or [E] + [ZA ₄ ]

In Formula 5 above,

E is a neutral or cationic Lewis base; H is a hydrogen atom;

Z is a group 13 element;

A may be the same or different from each other, and each independently represents an aryl group with 6 to 20 carbon atoms or an alkyl group with 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted or unsubstituted with halogen, a hydrocarbon with 1 to 20 carbon atoms, alkoxy, or phenoxy. .