KR20170035711A - Polypropylene resin composition having improved whitening resistance and high impact resistance - Google Patents

Abstract

The present invention relates to a thermoplastic polypropylene resin composition comprising: (a) 50 to 99 wt% of polypropylene (excluding atactic polypropylene); (b) 0.1 to 10 wt% of atactic polypropylene; and (c) 0.1 to 49.9 wt% of at least one additive, and a molded article made from the composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a polypropylene resin composition having improved whiteness and impact resistance. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

TECHNICAL FIELD The present invention relates to a thermoplastic polypropylene resin composition improved in whitening problem by mixing amorphous atactic polypropylene in a specific composition and a molded article using the same.

Polypropylene resins are widely used as materials for injection molding products because they are lightweight, have a low cost, have a high softening temperature, and have excellent mechanical properties such as tensile strength, bending strength and rigidity. In addition, the molded product has good transparency and surface gloss, and has excellent electrical characteristics, water resistance, and chemical resistance. Polypropylene, which has many advantages, has been applied in various fields from film packaging materials to small injection containers. However, as the product became larger, various problems appeared and some improvement points appeared.

That is, although the polypropylene homopolymer (homopolypropylene) has good impact resistance at room temperature, the impact resistance is not good at a low temperature of -5 ° C or lower, which causes problems in large-sized articles such as a vehicle bumper. In particular, weight reduction in consideration of the unit price while exhibiting a large size of the product shows weakness to the external impact, and there is a problem that the whitening resistance due to the bending and external impact is reduced. To improve the impact resistance by adding an impact modifier to the homopolypropylene as the above-mentioned problem, the stiffness of the resin is rapidly lowered as the content of the impact modifier increases. Also, although the physical properties are supplemented through the rubber-elastic body, the price of the product is increased. The rubber-elastic material effective for improving the impact resistance has a high viscosity, so that the addition of the rubber-elastic material to polypropylene deteriorates the processability during injection molding and the whitening phenomenon due to the difference in shrinkage ratio between the composition and the modifier. For example, US Pat. No. 5,285,464, US Pat. No. 4,734,459 and JP 5,202,744-6 / 77 disclose a method of adding a styrene-ethylene-butylene-styrene (SEBS) rubber or blending high density polyethylene However, problems such as deterioration of rigidity and heat resistance still can not be solved. In addition, Korean Patent Publication No. 1501835 discloses a method for improving the impact resistance and whitening resistance of a polypropylene resin by synthesizing an ethylene-propylene-butene terpolymer, and JP-A-2013-091786 discloses an ethylene- The method of enhancing the whitening resistance through the copolymer film has been proposed, but the whitening resistance measurement method is ambiguous and complicated. In particular, there has been no way to improve the whitening resistance while maintaining or enhancing the intrinsic properties of the crystalline polypropylene that has been commercialized in the past.

SUMMARY OF THE INVENTION The present invention has been conceived in order to solve the above-mentioned problems, and it is an object of the present invention to provide a thermoplastic resin composition containing a crystalline polypropylene, which is a mixture of amorphous polypropylene (aPP) To solve the whitening problem of conventional crystalline polypropylene.

Accordingly, it is an object of the present invention to provide a thermoplastic resin composition having improved whitening resistance and impact resistance by containing the above-mentioned amorphous polypropylene and conventional polypropylene at a specific composition ratio, and a molded article produced therefrom.

In order to achieve the above object, the present invention provides a polypropylene resin composition comprising (a) 50 to 99% by weight of polypropylene (excluding atactic polypropylene); (b) 0.1 to 10% by weight of atactic polypropylene; And (c) 0.1 to 49.9% by weight of at least one additive.

According to a preferred embodiment of the present invention, the polypropylene (a) is a propylene homopolymer; Block copolymers or graft copolymers of propylene and at least one or more olefin monomers, preferably crystalline homopolypropylene.

According to another preferred embodiment of the present invention, the atactic polypropylene (b) may satisfy the following conditions (i) to (iv).

(Ii) a molecular weight distribution (Mw / Mn) of 1 to 10; (iii) a weight average molecular weight distribution (Mw / Mn) The molecular weight (Mw) is 10,000 to 1,000,000, and (iv) the density is 0.8 to 0.9 g / ml.

The present invention also provides a molded article produced from the above-mentioned thermoplastic polypropylene resin composition.

In the present invention, by using atactic polypropylene (aPP) adjusted to a specific content as one component of the thermoplastic polypropylene resin composition, excellent whitening resistance and impact resistance can be exhibited. Therefore, the polypropylene composition can be usefully used as molded articles in various fields such as automobile interior / exterior materials and food packaging containers.

Hereinafter, the present invention will be described in detail.

Polypropylene (PP) is classified into Syndiotactic Polypropylene (sPP), Isotactic Polypropylene (iPP), and Atactic Polypropylene (aPP) according to its steric structure. Among them, sPP and iPP have been studied due to their excellent mechanical properties and thermal properties, whereas aPP, which is a kind of noncrystalline polymer, has a limited property due to disordered stereoregularity, and thus commercial development has been delayed relatively. These aPPs are separated in the process of recovery of the aliphatic solvent as a byproduct in the initial iPP production slurry process, or as a heterogeneous catalyst using an organoaluminum compound such as diethylaluminum chloride as a cocatalyst or as an activator with modified titanium (III) chloride . However, in the iPP process in which the stereoregularity is further improved, amorphous aPP is no longer produced as a by-product, and even if a low-crystallinity PP is produced according to the purpose, it is obtained by adding a comonomer.

On the other hand, the present inventors have developed atactic polypropylene (aPP) having a narrow molecular weight distribution ranging from high molecular weight to low molecular weight through a structural modification of the catalyst using a metallocene catalyst system (Korean Patent No. 10-1384412 ). However, the above literature focuses only on the production method of atactic polypropylene and the catalyst system applied thereto, and nothing about the use of actually produced atactic polypropylene has been mentioned at all.

Accordingly, the present invention relates to a crystalline polypropylene-containing thermoplastic resin composition containing a crystalline amorphous polypropylene (aPP), which is a component of a thermoplastic resin composition, To improve the whitening resistance and to commercialize the final product.

The atactic polypropylene (aPP) used in the present invention is effective to apply to the crystalline polypropylene having different MI because the molecular weight distribution is narrow and the MI is easy to control. In addition, since the same polypropylene composition is excellent in miscibility, it is possible to sufficiently improve the whitening problem due to the difference in the composition of the composition. In addition, when the above-mentioned atactic polypropylene (aPP) is mixed with the existing crystalline propylene, it is possible to minimize deterioration of inherent impact resistance properties of the crystalline propylene (see Tables 3 to 4 below).

Hereinafter, the chemical composition and physical properties of the thermoplastic polypropylene resin composition according to the present invention will be described in more detail. However, the present invention is not limited only to the following composition, and each composition may be modified or optionally mixed as necessary.

≪ Thermoplastic polypropylene resin composition >

The thermoplastic polypropylene resin composition of the present invention mainly comprises (a) polypropylene (except for atactic polypropylene); (b) atactic polypropylene (aPP); And at least one additive, wherein they are formulated in a particular composition.

(a) a polypropylene resin

As the first component constituting the polypropylene resin composition according to the present invention, conventional polypropylene resins known in the art can be used without limitation. However, non-crystalline atactic polypropylene (aPP) is excluded.

The polypropylene is a propylene homopolymer (homopolypropylene); Or a random copolymer, block copolymer or graft copolymer of propylene and at least one or more olefin monomers.

Here, the olefin monomer capable of forming a copolymer with propylene is not particularly limited, and monomers customary in the technical field of the present invention may be used.

Non-limiting examples of olefinic monomers that can be used include (C ₂ -C ₂₀ ) alpha-olefin, (C ₃ -C ₂₀ ) cycloolefin or (C ₃ -C ₂₀ ) Cyclohexane, cyclohexane, cyclohexane, cyclohexane, cyclohexane, cyclohexane, cyclohexane, cyclohexane, cyclohexane, Preferable examples of the olefin-based monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-pentene- 1-hexene) and C ₂ -C ₂₀ alpha-olefins including octene; C ₃ containing Cyclopentene, Cyclohexene, Cyclopentadiene, Cyclohexadiene, Norbonene and Methyl-2-Norbonene, C ₂₀ -cyclo-olefin or cyclodiolefin; Substituted styrene in which an alkyl group, an alkoxy group, a halogen group, an amine group, a silyl group, a haloalkyl group or the like is bonded to a benzene ring of styrene or styrene; Or a mixture thereof.

The polypropylene resin may be a conventional crystalline or low-crystalline polypropylene known in the art, preferably a crystalline homopolypropylene resin.

The weight average molecular weight (Mw) of the polypropylene resin is in the range of 10,000 to 1,000,000, preferably 50,000 to 900,000, and more preferably 100,000 to 800,000.

The polypropylene resin has a melt index (MI) of 0.01 to 100 g / 10 min (230 ° C), preferably 0.1 to 80 g / 10 min, and more preferably 0.5 to 60 g / 10 min.

In the thermoplastic polypropylene resin composition according to the present invention, the content of the polypropylene (a) is not particularly limited and may be, for example, in the range of 50 to 99.0% by weight based on 100% by weight of the total resin composition, Is in the range of 50 to 90% by weight. When the polypropylene resin falls within the above-mentioned content range, it can exhibit stable physical properties in terms of moldability and hardness.

(b) Atactic polypropylene (aPP) resin

The second component constituting the polypropylene resin composition according to the present invention is an amorphous atactic polypropylene (aPP) resin.

The atactic polypropylene (aPP) has significantly lower crystallinity than conventional syndiotactic polypropylene (sPP) or isotactic PP, and exhibits flexibility, impact resistance and low shrinkage due to its low hardness. At the same time, it has softness comparable to rubber but has a relatively stronger heat resistance than rubber. In the present invention, by adding the aforementioned atactic polypropylene in a specific content range, not only the whitening resistance of the conventional crystalline polypropylene can be improved, but also the impact resistance effect exhibited by conventional crystalline polypropylene can be exerted equally.

The atactic polypropylene (aPP) used in the present invention has a stereoregularity (pentad II, mmmm) of 5 to 20%, preferably 5 to 10. The molecular weight distribution (Mw / Mn) is 1 to 20, preferably 1 to 10. [ The weight average molecular weight (Mw) of the atactic polypropylene (aPP) is 10,000 to 1,000,000, preferably 20,000 to 900,000, more preferably 100,000 to 800,000, the density is 0.9 g / ml or less, Is 0.8 to 0.9 g / ml, more preferably 0.8 to 0.880 g / ml.

In the thermoplastic polypropylene resin composition according to the present invention, the content of the atactic polypropylene (b) is not particularly limited and may be, for example, in the range of 0.1 to 10% by weight based on 100% by weight of the total resin composition, Preferably 1 to 8% by weight, and more preferably 1 to 6% by weight. When the polypropylene resin falls within the above-mentioned content range, it is possible to exhibit an excellent whitening effect without deteriorating the impact resistance of the existing crystalline polypropylene.

On the other hand, the atactic polypropylene is preferably prepared by polymerizing propylene in the presence of a transition metal catalyst represented by the following general formula (1). Such a transition metal catalyst is a transition metal compound having a thiophene fused ring compound as a ligand bonded to a central metal while having a group 3 to 10 metal in the periodic table as a central metal.

In Formula 1,

M is a transition metal selected from the group consisting of Group 4 elements on the periodic table;

Q ¹ and Q ² are the same or different and are each halogen, (C ₁ -C ₂₀₎ alkyl, (C ₂ -C ₂₀₎ alkenyl, (C ₂ -C ₂₀₎ alkynyl, independently, (C ₆ -C ₂₀₎ aryl, (C ₁ -C ₂₀₎ alkyl (C ₆ -C ₂₀₎ aryl, (C ₆ -C ₂₀₎ aryl (C ₁ -C ₂₀₎ alkyl, (C ₁ -C ₂₀₎ alkyl amido , (C ₆ -C ₂₀ ) arylamido, and (C ₁ -C ₂₀ ) alkylidene;

R ¹ to R ¹⁰ are the same as or different from each other, and each independently hydrogen; (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Acetal, which does not include or include a ketal or ether (C ₂ -C ₂₀₎ alkenyl; (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl, with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Or (C ₁ -C ₂₀ ) silyl, with or without an acetal, ketal or ether group; In this case, R ¹ and R ² , or R ³ and R ⁴ may be connected to each other to form a ring, and two or more of R ⁵ to R ¹⁰ may be connected to each other to form a ring;

R ¹¹ to R ¹³ are the same as or different from each other, and each independently hydrogen; (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Acetal, which does not include or include a ketal or ether (C ₂ -C ₂₀₎ alkenyl; (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl, with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; (C ₁ -C ₂₀ ) silyl with or without an acetal, ketal or ether group; (C ₁ -C ₂₀₎ alkoxy; And (C ₆ -C ₂₀₎ is selected from the group consisting of aryloxy; Wherein R < ¹¹ > and R < ¹² & Or R ¹² and R ¹³ may be connected to each other to form a ring.

The transition metal catalyst compound represented by the general formula (1) is a compound in which an amido ligand and ortho-phenylene form a condensed ring and the pentagonal ring pi-ligand bonded to the ortho-phenylene is fused with a thiophene heterocycle And includes a ligand of a new structure. Accordingly, the transition metal catalyst compound has an advantage in that the polymerization activity of propylene is higher than that of the transition metal compound in which the thiophene hetero ring is not fused.

In the compound represented by the general formula (1), R ¹ to R ¹³ may be the same or different and each independently substituted with a substituent including an acetal, ketal or ether group. When the substituent is substituted with such a substituent, it may be more advantageous to carry it on the surface of the carrier.

According to a preferred embodiment of the present invention, M in the formula (1) is preferably titanium (Ti), zirconium (Zr) or hafnium (Hf).

Q ¹ and Q ² are the same or different and each independently is preferably a halogen or (C 1 -C 20) alkyl group, more preferably chlorine or methyl.

In addition, R ¹ to R ⁵ may be the same or different and each independently hydrogen or a (C ₁ -C ₂₀ ) alkyl group, and preferably each independently hydrogen or methyl. More preferably, R ¹ to R ⁵ are each independently hydrogen or methyl, provided that at least one of R ³ and R ⁴ is methyl and R ⁵ is methyl.

In the compounds represented by the above formula (1), it is preferable that R ⁶ to R ¹³ are each independently hydrogen. The transition metal compound represented by Formula 1 preferably includes the substituents described above for controlling the electronic and stereoscopic environment around the metal.

According to a preferred embodiment of the present invention, the catalyst system containing the transition metal catalyst as a main catalyst further comprises a cocatalyst compound.

The promoter compound is mixed with the main catalyst compound or supported on the carrier to activate the main catalyst compound. Therefore, the catalyst can be used without limitation as long as it is a promoter compound capable of activating the main catalyst compound without lowering the activity of the supported catalyst according to the present invention.

More specifically, the promoter compound of the present invention may be represented by any one of the compounds represented by the following formulas (2) to (4). The cocatalyst represented by the general formulas (2) to (4) activates the main catalyst compound represented by the general formula (1). That is, it serves to cationize or activate the central metal (M) of the main catalyst transition metal compound so that propylene reacts well with the core metal.

(2)

^{- [Al (R 21) -O} ] a -

(3)

D ( ^R31 ) 3

[Chemical Formula 4]

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

In the above Chemical Formulas 2 to 4,

R < ²¹ > are each independently a halogen radical; (C ₁ -C ₂₀ ) hydrocarbyl radical; Or a (C ₁ -C ₂₀ ) hydrocarbyl radical substituted with halogen; a is an integer of 2 or more, for example, 2 to 50;

D is aluminum or boron;

R ³¹ are each independently a halogen radical; (C ₁ -C ₂₀ ) hydrocarbyl radical; Or a (C ₁ -C ₂₀ ) hydrocarbyl radical substituted with halogen;

L is a neutral or cationic Lewis acid;

Z is an element selected from the group consisting of Group 13 elements on the periodic table;

A are each independently substituted by 1 or more hydrogen atoms are halogen, (C ₁ -C ₂₀₎ hydrocarbyl, (C ₁ -C ₂₀₎ alkoxy, or (C ₆ -C ₂₀₎ aryloxy radical, (C ₆ - C ₂₀₎ aryl or (C ₁ -C ₂₀₎ alkyl radical.

The compounds represented by the general formulas (2) to (4) are compounds widely used as a cocatalyst for a homogeneous Ziegler catalyst containing a metallocene compound. The promoter compounds of the general formulas (2) to (4) have strong electrophilicity and rapidly dissociate Q ¹ and / or Q ² bound to the central metal M of the main catalyst compound represented by the general formula (1). At this time, the polymerization activity increases as Q ¹ and / or Q ² dissociate rapidly, and the longer the time for stabilization of the center metal M, the longer the coordination of the stabilized M with the double bond contained in propylene The amorphous polypropylene polymer having a high molecular weight and a low density can be obtained.

In particular, according to the present invention, it is preferable that R ²¹ in the above formula (2) is methyl, ethyl, n-butyl or isobutyl so that the above-mentioned co-catalyst compound can exhibit a better activation effect; In Formula 3, D is aluminum and R ³¹ is methyl or isobutyl, or D is boron and R ³¹ is preferably pentafluorophenyl; In Formula 4 [LH] ⁺ is dimethylanilinium not dimethyl _{cation, [Z (A) 4]} - is _{[B (C 6 F 5)} 4] - a, [L] ⁺ is [(C ₆ H _{5) 3} C] ⁺ .

In the present invention, the addition amount of the promoter compound may be determined in consideration of the addition amount of the main catalyst compound represented by the formula (1), the amount necessary for sufficiently activating the co-catalyst compound, and the like.

According to a preferred embodiment of the present invention, the promoter compound may be contained in a molar ratio of 1: 1 to 100,000, preferably 1: 1 to 10,000, more preferably 1: 1 to 5,000, relative to the main catalyst compound.

More specifically, the molar ratio (M: Al) of the promoter compound represented by Formula 2 to the transition metal compound represented by Formula 1 is preferably 1: 100 to 1: 20000, more preferably 1: 500 to 1: 1: 5000.

The molar ratio (M: D) of the promoter compound of the formula (3) to the transition metal compound represented by the formula (1) is not particularly limited, but is preferably 1: 1 to 1:10 when D is boron. Preferably 1: 1 to 1: 3. Also, when D is Al, it may vary depending on the amount of water in the polymerization system, but is usually in the range of 1: 1 to 1: 1000, more preferably in the range of 1: 1 to 1: 100.

The molar ratio (M: Z) of the promoter compound of Formula 4 to the transition metal compound represented by Formula 1 is preferably in the range of 1: 1 to 1:10, more preferably 1: 1 to 1: 4 . In the present invention, when the molar ratio of the cocatalyst compound to the transition metal compound represented by the formula (1) is lower than the lower limit value described above, there is a possibility that the catalyst is not activated. When the molar ratio is higher than the upper limit value, .

The compound represented by Formula 2 is a conventional aluminoxane compound having a chain or cyclic or network structure. Non-limiting examples thereof include Methylaluminoxane, Ethylaluminoxane, Butylaluminoxane, Hexylaluminoxane, Octylaluminoxane, Decylaluminoxane, and the like .

Examples of organoaluminum compounds represented by Formula 3 include, but are not limited to, trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, Trialkyl aluminum such as trioctylaluminum and tridecylaluminum, a dialkylaluminum alkoxide such as dimethylaluminum methoxide, diethylaluminum methoxide and dibutylaluminum methoxide, Dialkylaluminum alkoxides such as dialkylaluminum alkoxide, dimethylaluminum chloride, diethylaluminum chloride and dibutylaluminum chloride, and dialkylaluminum alkoxides such as methylaluminum alkylaluminum dialkoxides such as ethylaluminum dimethoxide, ethylaluminum dimethoxide and butylaluminum dimethoxide, methylaluminum dichloride, ethylaluminum dichloride, , And alkylaluminum dihalide such as butylaluminum dichloride.

The compound represented by Formula 4 is a Bulky compound that reacts with a transition metal compound to make the transition metal compound catalytically active. Non-limiting examples of the compound include trimethylammonium tetrakis (pentafluoro (Pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, and tripropylammonium tetrakis pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, ttri (n-butyl) ammonium tetrakis ) N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) N, N-dimethylanilinium n-butyltris (pentafluorophenyl) borate), N, N-dimethylanilinium benzyltris (pentafluorophenyl) (Pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluoro N, N-dimethylanilinium tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis Silyl) -2,3,5,6-tetrafluorophenyl) borate (N, N-dimethylanilinium tetrakis (4- (triisopropysilyl) -2,3,5,6-tetrafluorophenyl) N, N-dimethylanilinium pentafluorophenoxytris (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borane (Pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) trimethylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylammonium tetrakis (2,3,5,6-tetrafluorophenyl) borate, N , N-diethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, Tripropylammonium tetrakis (2,3,4,6-tetrafluorophcnyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluoropheny N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate), N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate (N, N-diethylanilinium tetrakis) Dimethyl 2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate (N, N-dimethyl-2,4,6-trimethylanilinium tetrakis -tetrafluorophenyl) borate).

Non-limiting examples of the dialkylammonium include di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate (di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate), dicyclohexylammonium tetrakis (Pentafluorophenyl) borate), and the like.

Nonlimiting examples of trialkylphosphonium include triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (o-tolylphosphonium tetrakis (pentafluorophenyl) borate tri tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, and the like. In the present invention,

Also, non-limiting examples of dialkyloxonium include diphenyloxonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) oxonium tetrakis (pentafluorophenyl) Di (2,6-dimethylphenyl oxonium tetrakis (pentafluorophenyl) borate), di (2,6-dimethylphenyloxonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) oxonium tetrakis .

Also, non-limiting examples of the dialkylsulfonium include diphenylsulfonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) Bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, borate). At this time, the promoter compound according to the present invention is not limited to the above examples, and propylene may be used singly or in combination of two or more.

In the present invention, the main catalyst compound and the cocatalyst compound may be used in the form of a supported catalyst supported on a carrier.

The carrier is not particularly limited as long as it can support the main catalyst and the cocatalyst compound component as described above. For example, porous organic compounds, inorganic compounds, or complexes thereof having fine pores on the surface or inside thereof can be applied without limitation to those which are conventional in the technical field of the present invention.

Examples of the inorganic compound include silica, alumina, magnesium chloride (MgCl ₂ ), calcium chloride (CaCl ₂ ), bauxite, xeolite, magnesium oxide (MgO), zirconium oxide ZrO ₂ ), titanium oxide (TiO ₂ ), boron trioxide (B ₂ O ₃ ), calcium oxide (CaO), zinc oxide (ZnO), barium oxide (BaO), thorium oxide (THO ₂ ) However, the present invention is not limited thereto. Particular examples of the composite _{SiO 2 -MgO, SiO 2 -Al 2} O 3, SiO 2 -TiO 2, SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO 2 -MgO And so on. Examples of the organic compound include starch, cyclodextrin, synthetic polymer, and the like, but are not limited thereto. These carriers may be used alone or in combination of two or more.

The method of supporting the main catalyst compound and the cocatalyst compound on the carrier is not particularly limited. For example, (i) a method of directly supporting a mixture of the main catalyst compound and the promoter compound on a dehydrated carrier; (Ii) a method in which the carrier is pretreated with the co-catalyst compound and then the main catalyst compound is supported thereon; (Iii) supporting the main catalyst compound on the support and then treating the support with a co-catalyst compound; (Iv) a method in which the main catalyst compound and a cocatalyst compound are reacted and then supported on a carrier may be applied.

At this time, in the method of supporting the main catalyst compound and the co-catalyst compound, the main catalyst and the cocatalyst may be carried sequentially, or the order of the main catalyst and the cocatalyst may be changed and carried, and further, To be mixed.

The polymerization step of the atactic polypropylene (b) according to the present invention can be carried out in a slurry phase, a liquid phase, a gaseous phase or a bulk phase process. When the above polymerization step is carried out in a liquid phase or a slurry, a solvent, a polypropylene or an olefin-based monomer itself can be used as a medium.

Examples of the solvent usable in the polymerization step include butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, Aliphatic hydrocarbon solvents such as undecane, dodecane, cyclopentane, methylcyclopentane, and cyclohexane; Aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene and chlorobenzene; aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene and chlorobenzene; Halogenated aliphatic hydrocarbons such as dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, and 1,2-dichloroethane, menstruum; Or a mixture thereof.

The polymerization may be performed in a batch type, a semi-continuous type, or a continuous type.

In the present invention, the temperature and pressure conditions of the polymerization reaction can be determined in consideration of the efficiency of the polymerization reaction depending on the kind of the reaction to be applied and the kind of the reactor. In one example, the polymerization temperature may be from -50 to 500 占 폚, preferably from 0 to 400 占 폚, and the pressure may be from 1 to 3000 atm, preferably from 1 to 1000 atm.

In the meantime, the amorphous polypropylene according to the present invention can easily control the microstructure of the polymer by using the above-mentioned catalyst, and can produce a polypropylene having a high molecular weight and a low density.

The density of the atactic polypropylene thus produced may be 0.8 to 0.9 g / ml, preferably 0.8 to 0.880 g / ml, more preferably 0.82 to 0.880 g / ml.

In addition, the above-mentioned atactic polypropylene may have a stereoregularity (isotacticity, Pentad I.I, mmmm) of 5 to 20%, preferably 5 to 18%, more preferably 5 to 15%.

The molecular weight distribution (Mw / Mn) of the atactic polypropylene according to the present invention may be 1 to 10, preferably 1.5 to 8, more preferably 2 to 6. In addition, the weight average molecular weight (Mw) may be 10,000 to 1,000,000, preferably 20,000 to 900,000, and more preferably 50,000 to 800,000.

Meanwhile, the method for producing atactic polypropylene according to the present invention may be carried out in addition to the above-mentioned steps, further including steps that can be carried out conventionally in the art before or after the above step, The manufacturing method of the present invention is not limited thereto.

(c) Additive

The third component constituting the polypropylene resin composition according to the present invention is a common additive component used in the polypropylene resin composition in this field.

The additive is not particularly limited to the components and uses thereof, and examples of the additives include a nucleating agent, a colorant, an MI synergist, an antioxidant, a catalyst neutralizer, a pigment, a dispersant, a lubricant, an antistatic agent, a UV stabilizer, a slip agent, A filler or a mixture of at least one of these may be used.

In the thermoplastic polypropylene resin composition according to the present invention, the content of the one or more additives (c) is not particularly limited, and may be a residual amount satisfying 100 wt% of the total weight of the thermoplastic polypropylene resin composition. For example, 0.1 to 49.9% by weight, preferably 1 to 10% by weight, more preferably 1 to 5% by weight based on 100% by weight of the total resin composition.

For example, the nucleating agent may be a conventional component known in the art. More specifically, the nucleating agent may be an organic metal-based nucleating agent such as aluminum paracetylbutylbenzoic acid, sodium benzoate, calcium benzoate, benzylidene sorbitol, methylbenzylidene sorbitol , Ethylbenzylidene sorbitol, 3,4-dimethylbenzylidene sorbitol and the like, and a surfactant such as 1,2,3-trideoxy-4,6: 5,7-bis-O - [(4-propylphenyl) methylene ] -Nonitol, and the like. Specific examples of the nucleating agent include Adeka Mark NA-11 in the phosphate system, Mitsui Toatsu NC-4 and Milliken Millad 3988 in the sorbitol system, and Shell GB (AL-PTBBA) in the aluminum system.

The colorant may also be a conventional component known in the art, and more particularly, it may be at least one selected from the group consisting of titanium-based oxides such as titanium and dioxide.

Also, non-limiting examples of usable MI (Melt Index) synergists include at least one selected from the group consisting of organic peroxides such as bis (t-butylperoxyisopropyl) benzene and the like.

Antioxidants can be used without limitation in conventional antioxidant components known in the art, including but not limited to tetrakis (methylene (3,5-di-t-butyl-4-hydroxy) hydrosilylate) And phenol-based antioxidants such as 1,3,5-trimethyl-tris (3,5-di-t-butyl-4-hydroxybenzene) and tris (2,4-di-t-butylphenol) A phosphite-based antioxidant, and the like.

More specifically, examples of the antioxidant include phenol-based, phosphite-based, and thioester-based antioxidants. Specific examples of the phenol include Ciba IRGANOX 1010, Ciba IRGANOX 1076, Yoshitomi BHT, Ciba IRGANOX 3114, Ciba IRGANOX 1330, Ciba IRGANOX MD1024, BHT, SONGNOX 1290, SONGNOX 2246, SONGNOX 4425, SONGNOX 2500, SONGNOX 1076, SONGNOX 1010, SONGNOX 2450, SONGNOX 3114, SONGNOX 1035, SONGNOX 4150, SONGNOX 1330, SONGNOX 1024, SONGNOX 2590, SONGNOX 1098, SONGNOX 1135 and SONGNOX 1077. Specific examples of the phosphite system include Ciba IRGAFOS 168, GE ULTRANOX 626, GE ULTRANOX 641, Ciba IRGAFOS P-EPQ, Songnox 1680, and the like. Specific examples of the thioester system include Ciba IRGANOX PS 800, Ciba IRGANOX PS 802, and the like.

The catalyst neutralizing agent may be at least one of conventional organic catalyst neutralizing agents and inorganic catalyst neutralizing agents known in the art, and is preferably calcium stearate or hydrotalcite. Specific examples of the neutralizing agent include Songwon SC-110 (METAL SOAP) and HYDROTALCITE.

The polypropylene resin composition excellent in whitening resistance and impact resistance according to the present invention can contain pigments, dispersants, endurance agents, antistatic agents, UV stabilizers, antistatic agents, antistatic agents, Slip agents, anti-blocking agents, inorganic fillers, and the like.

The inorganic filler may be included for the purpose of improving the thermal deformation of the thermoplastic resin composition and the molded article thereof and increasing the rigidity thereof. Non-limiting examples thereof include talc, calcium carbonate, calcium sulfate, magnesium oxide, calcium stearate, mica, silica, calcium silicate, clay, carbon black and the like.

The present invention also provides a molded article produced using the above-mentioned polypropylene resin composition.

The molded article made from the polypropylene resin composition according to the present invention can be manufactured by molding by extrusion, blow molding, film molding, injection molding, vacuum molding, etc., but is not limited thereto. In addition, the molded article is not particularly limited in its application field. For example, it can be used without limitation in automobile interior / exterior materials, multipurpose storage boxes, refrigerated / frozen food storage products, transparent sheets, food storage, Household appliances and transparent appliances.

More specifically, it may be a refrigerated container, a freezing container, a multipurpose container, an automobile interior and exterior material, a food packaging container, a bottle cap, a packaging film, a protective film, a decor sheet, a retort pouch,

Hereinafter, the present invention will be described in more detail with reference to examples.

The present invention is not limited to the embodiments described below, but may be embodied in other forms. The embodiments disclosed herein are provided so that the disclosure may be thorough and complete, and that those skilled in the art will be able to convey the spirit of the invention to those skilled in the art. Therefore, the present invention should not be limited by the following examples.

[Synthesis Example 1] Synthesis of Compound 4

For reference, the synthesis reaction proceeded in an inert atmosphere such as nitrogen or argon, and standard Schlenk technique and glove box technique were used.

More specifically, a Schlenk flask containing 1,2,3,4-tetrahydroquinoline (1.00 g, 7.51 mmol) and diethyl ether (16 mL) was dipped in a low-temperature bath at -78 ° C, Butyl lithium (3.0 mL, 7.5 mmol, 2.5 M hexane solution) was slowly injected under a nitrogen atmosphere. After stirring at -78 ° C for about one hour, the temperature was slowly raised to room temperature. A pale yellow solid precipitated and the butane gas produced was removed through a bubbler. The temperature was again lowered to -78 ° C and then carbon dioxide was injected. As soon as the carbon dioxide was injected, the solution in the slurry state became a transparent uniform solution. After stirring at -78 ° C for about one hour, the excess carbon dioxide was removed through a bubbler while slowly raising the temperature to -20 ° C. The white solid precipitated again. Tetrahydrofuran (0.60 g, 8.3 mmol) and t-butyllithium (4.9 mL, 8.3 mmol, 1.7 M pentane solution) were successively introduced under nitrogen atmosphere at -20 ° C and stirred for about two hours. Then, a tetrahydrofuran solution (19 mL) in which lithium chloride and the following compound 1 (1.06 g, 6.38 mmol) was dissolved was introduced under a nitrogen atmosphere. After stirring at -20 ° C for one hour, the temperature was slowly raised to room temperature. After stirring at room temperature for one hour, water (15 mL) was added to terminate the reaction. The solution was transferred to a separatory funnel to extract the organic layer. The extracted organic layer was put back into a separatory funnel, and then hydrochloric acid (2 N, 40 mL) was added thereto. After shaking for about 2 minutes, aqueous sodium bicarbonate (60 mL) was slowly added to neutralize. The organic layer was separated, dried over anhydrous magnesium sulfate, and then the solvent was removed to obtain a viscous material. The compound was purified by a silica gel column chromatography method using a mixed solvent of hexane and ethyl acetate (v / v, 50: 1) to obtain 77.2 mg of a compound (yield: 43%).

^{The 1} H NMR analysis showed that two signal sets were observed at 1: 1 because of the inability to rotate about the carbon-carbon bond (the bolded bond in Scheme 1 below) that weaves phenylene and cyclopentadiene do. Further, the values in parentheses in the following ¹³ C NMR data are the chemical shift values of the divided signals due to the fact that the rotation is not easy.

_{^{1 H NMR (C 6 D 6}} ): δ 7.22 and 7.17 (br d, J = 7.2Hz, 1H), 6.88 (s, 2H), 6.93 (d, J = 7.2Hz, 1H), 6.73 (br t, 2H, CH2), 2.65-2.55 (q, J = 7.2 Hz, 1H), 3.84 and 3.80 2H, CH 2), 1.87 (s, 3H, CH 3), 1.70-1.50 (m, 2H, CH 2), 1.16 (d, J = 8.0 Hz, 3H, CH 3) ppm.

¹³ C {1H} NMR (C ₆ D ₆ ): 151.64 (151.60), 147.74 (147.61), 146.68, 143.06, 132.60, 132.30, 129.85, 125.02, 121.85, 121.72, 119.74, 116.87, 45.86, 42.54, 28.39, 22.89 , 16.32, 14.21 ppm.

[Chemical Formula 5]

R ^b R ^c Compound 1 H H Compound 2 Me Me Compound 3 Me H

[Synthesis Example 2] Synthesis of Compound 5

Compound 2 was used instead of Compound 1 to synthesize Compound 4 according to the same conditions as in Synthesis Example 1. The yield was 53%.

¹ H NMR analysis showed that two signal sets were observed at 1: 1, which is due to the inability to rotate about the carbon-carbon bond (the bolded bond in scheme 1) that weaves phenylene and cyclopentadiene.

_{1 H NMR (C 6 D 6} ): δ 7.23 (d, J = 7.2Hz, 1H), 6.93 (d, J = 7.2Hz, 1H), 6.74 (br t, J = 7.2Hz, 1H), 4.00 and (Br, 2H, CH 2), 2.16 (s, 1H), 3.93 (s, 3H, CH3), 2.04 (br s, 3H, CH3), 1.91 (s, 3H, CH3), 1.75-1.50 (m, 2H, CH2), 1.21 (d, J = 8.0Hz,

13C {1H) NMR (C6D6): 151.60 (151.43), 145.56 (145.36), 143.08, 141.43, 132.90, 132.68, 132.43, 129.70, 121.63, 120.01, 116.77, 46.13, 42.58, 28.42, 22.97, 15.06, 14.19, 14.08 , 12.70 ppm.

[Synthesis Example 3] Synthesis of Compound 6

Tetrahydroquinoline was used instead of Tetrahydroquinoline to synthesize Compound 4 of Synthesis Example 1 by the same conditions and procedures as those of Synthesis Example 1. The yield was 63%.

¹ H NMR analysis showed that the signal was separated into four signals with a ratio of 1: 1: 1: 1 in any signal, indicating that rotation about the carbon-carbon bonds connecting phenylene and cyclopentadiene was not easy, Due to the existence of the chiral centers.

^{1 H NMR (C6D6): δ} 7.33, 7.29, 7.22, and 7.17 (d, J = 7.2Hz, 1H), 6.97 (d, J = 7.2Hz, 1H), 6.88 (s, 2H), 6.80 - 6.70 ( (m, 2H, CH2), 1.91, 1.89, and 1.86 (s, 3H), 3.93-3.86 (s, 1H, NH), 3.20-2.90 (m, 2H, NCHMe, CHMe), 2.90-2.50 , CH3), 1.67-1.50 (m, 1H, CH2), 1.50-1.33 (m, 1H, CH2), 1.18, 1.16, and 1.14 (s, 3H, CH3), 0.86, 0.85, = 8.0 Hz, 3H, CH3) ppm.

¹³ C {1H} NMR (C6D6): 151.67, 147.68 (147.56, 147.38), 147.06 (146.83,146.28,146.10), 143.01 (142.88), 132.99 (132.59), 132.36 (131.92), 129.69,125.26 , 124.83), 122.03,121.69 (121.60, 121.28), 119.74 (119.68, 119.46), 117.13 (117.07,116.79,116.72), 47.90 (47.73), 46.04 (45.85), 31.00 (30.92, 30.50), 28.00 27.64), 23.25 (23.00), 16.38 (16.30), 14.63 (14.52, 14.18) ppm.

[Synthesis Example 4] Synthesis of Compound 7

Synthesis was carried out by the same conditions and procedures as in the synthesis of the compound 4 of the above Synthesis Example 1 except that tetrahydroquinaline was used instead of tetrahydroquinoline and Compound 2 was used instead of the compound 1. The yield was 63%.

^{As a} result of ¹ H NMR analysis, 4 signals of 1: 1: 1: 1 ratio were observed for any signal, indicating that rotation about the carbon-carbon bond connecting phenylene and cyclopentadiene was not easy Due to the existence of two chiral centers.

^{1 H NMR (C6D6): δ} 7.32, 7.30, 7.22, and 7.19 (d, J = 7.2Hz, 1H), 6.97 (d, J = 7.2Hz, 1H), 6.85 - 6.65 (m, 1H), 4.10 - 2H, CH2), 2.15 (s, 3H, CH3), 2.02 (s, 3H, CH3), 3.90 (s, 1H, NH), 3.30-2.85 (m, 2H, NCHMe, CHMe), 2.85-2.50 , 1.94, 1.92, and 1.91 (s, 3H, CH3), 1.65-1.50 (m, 1H, CH2), 1.50-1.33 (m, 1H, CH2), 1.22, 1.21, 1.20, CH3), 1.10-0.75 (m, 3H, CH3) ppm.

¹³ C {1H} NMR (C6D6): 151.67 (151.57), 145.58 (145.33, 145.20), 143.10 (143.00, 142.89), 141.62 (141.12), 134.08 (133.04), 132.84 , 129.54, 121.52 (121.16), 119.96 (119.71), 117.04 (116.71), 47.90 (47.78), 46.29 (46.10), 31.05 (30.53), 28.02 (28.07), 23.37 (23.07), 15.22 14.02, 14.21), 12.72 (12.67) ppm.

[Synthesis Example 5] Synthesis of Compound 8

Synthesis was carried out by the same conditions and procedures as in the synthesis of the compound 4 of the above Synthesis Example 1 except that tetrahydroquinaline was used instead of tetrahydroquinoline and Compound 3 was used instead of the compound 1. The yield was 48%.

^{As a} result of ¹ H NMR analysis, 4 signals of 1: 1: 1: 1 ratio were observed for any signal, indicating that rotation about the carbon-carbon bond connecting phenylene and cyclopentadiene was not easy Due to the existence of two chiral centers.

^{1 H NMR (C6D6): δ} 7.32, 7.29, 7.22 and 7.18 (d, J = 7.2 Hz, 1H), 6.96 (d, J = 7.2 Hz, 1H), 6.84-6.68 (m, 1H), 6.60 (d 2H, CH2), 2.27 (s, 3H, < RTI ID = 0.0 > CH3), 1.94, 1.91 and 1.89 (s, 3H, CH3), 1.65-1.54 (m, 1H, CH2), 1.54-1.38 (m, 1H, CH2), 1.23, 1.22, ), 1.00-0.75 (m, 3H, CH3) ppm.

¹³ C {1H} NMR (C6D6): 151.51, 145.80, 145.64, 145.45, 144.40, 144.22, 143.76, 143.03, 142.91, 139.78, 139.69, 139.52, 133.12, 132.74, 132.52, 132.11, 129.59, 121.52, 121.19, 120.75, 120.47, 119.87, 119.69, 116.99, 116.76, 47.90, 47.77, 46.43, 46.23, 32.55, 30.98, 30.51, 27.95, 27.67, 23.67, 23.31, 23.06, 16.52, 15.01, 14.44, 14.05 ppm.

[Synthesis Example 6] Synthesis of titanium compound 9 < Catalyst 1 >

In a dry box, Compound 4 (0.10 g, 0.36 mmol) synthesized in Synthesis Example 1 and diethyl ether were placed in a round bottom flask, and the temperature was lowered to -30 ° C. N-Butyllithium (2.5 M hexane solution, 0.2 g, 0.71 mmol) was slowly added while stirring the flask and reacted at -30 캜 for two hours. The reaction was carried out with stirring for 3 hours while raising the temperature to room temperature. After the temperature was lowered to -30 캜, methyllithium (1.6 M diethyl ether solution, 0.33 g, 0.71 mmol) was added and TiCl ₄ DME (DME; dimethoxyethane, 0.10 g, 0.36 mmol) . After stirring for three hours while raising the temperature to room temperature, the solvent was removed using a vacuum line. The compound was extracted using pentane. The solvent was removed to obtain 0.085 g of a brown powdery compound (60%).

^{1 H NMR (C6D6): δ} 7.09 (d, J = 7.2Hz, 1H), 6.91 (d, J = 7.2Hz, 1H), 6.81 (t, J = 7.2Hz, 1H), 6.74 (s, 2H) 2H, CH2), 2.20 (s, 3H), 4.55 (dt, J = 14,2 5.2 Hz, 1H, NCH2), 4.38 (dt, J = 14,2 5.2 Hz, 1H, NCH2), 2.50-2.30 , 1.68 (s, 3H), 1.68 (quintet, J = 5.2 Hz, CH2), 0.72 (s, 3H, TiMe), 0.38 (s, 3H, TiMe) ppm.

¹³ C {1H} NMR (C6D6): 161.46, 142.43, 140.10, 133.03, 130.41,129.78,127.57,127.34,121.37,120.54,201.51,20,34,121.52,58.50,57.73,49.11,27.59,23.27,13.19,13.14 ppm .

[Synthesis Example 7] Synthesis of titanium compound 10 < Catalyst 2 >

Was synthesized in the same manner as in the synthesis of the compound 9 of the above Synthesis Example 6, except that the compound 5 prepared in Synthesis Example 2 was used instead of the above-mentioned Compound 4. The yield was 53%.

^{1 H NMR (C6D6): δ} 7.10 (d, J = 7.2Hz, 1H), 6.91 (d, J = 7.2Hz, 1H), 6.81 (t, J = 7.2Hz, 1H), 4.58 (dt, J = 2H, CH2), 2.32 (s, 3H), 2.11 (s, 3H), 2.42 (d, , 2.00 (s, 3H), 1.71 (s, 3H), 1.67 (quintet, J = 5.2 Hz, CH2), 0.72 (s, 3H, TiMe), 0.38 (s, 3H, TiMe) ppm.

¹³ C {1H} NMR (C6D6): 161.58, 141.36, 138.41, 137.20, 132.96,129.70,127.53,127.39,126.87,121.48,120.37,120.30,113.23,56.50,53.13,49.03,27.64,23.34,14.21,13.40, 12.99, 12.94 ppm. Anal. Calc. (C22H27N5O): C, 68.56; H, 7.06; N, 3.63. Found: C, 68.35H, 7.37N, 3.34%.

[Synthesis Example 8] Synthesis of titanium compound 11 < Catalyst 3 >

Was synthesized in the same manner as in the synthesis of the compound 9 of the above Synthesis Example 6, except that the Compound 6 prepared in Synthesis Example 3 was used instead of the above-mentioned Compound 4. The yield was 51%. 1: 1 ratio by the direction of the thiophene ring and the direction of the methyl group attached to the tetrahydroquinoline.

^{1 H NMR (C6D6): δ} 7.11 and 7.08 (d, J = 7.2Hz, 1H), 6.96 and 6.95 (d, J = 7.2Hz, 1H), 6.82 and 6.81 (t, J = 7.2Hz, 1H), 1H), 6.74 and 6.76 (d, J = 7.2 Hz, 1H), 6.74 and 6.73 (d, J = 7.2 Hz, 1H) 2H, CH 2), 1.17 and 1.15 (d, J = 4.8 Hz, 3H), 1.85-1.50 (m, ), 0.76 and 0.70 (s, 3H, TiMe), 0.42 and 0.32 (s, 3H, TiMe) ppm.

¹³ C {1H} NMR (C6D6): 159.58, 159.28, 141.88, 141.00, 139.63,138.98,134.45,130.85,131.50,129.59,129.50,129.47,127.23,127.20,127.17,127.11,201.77,20.70,201. 119.96, 119.91, 118.76, 118.57, 113.90, 110.48, 59.61, 56.42, 55.75, 51.96, 50.11, 49.98, 27.41, 27.11, 21.89, 20.09, 19.67, 12.94, 12.91, 12.65 ppm.

[Synthesis Example 9] Synthesis of titanium compound 12 < Catalyst 4 >

Was synthesized in the same manner as in the synthesis of the compound 9 of the above Synthesis Example 6, except that the compound 7 prepared in Synthesis Example 4 was used instead of the above-mentioned Compound 4. The yield was 57%. 1: 1 ratio by the direction of the thiophene ring and the direction of the methyl group attached to the tetrahydroquinoline.

^{1 H NMR (C6D6): δ} 7.12 and 7.10 (d, J = 7.2Hz, 1H), 6.96 and 6.94 (d, J = 7.2Hz, 1H), 6.82 and 6.81 (t, J = 7.2Hz, 1H), 2H), 2.45 (s, 3H), 2.10 (s, 3H), 1.97 (s, 3H), 1.75 and 1.66 (s, 3H), 1.85-1.50 (m, 2H, CH2), 1.20 (d, J = 6.8Hz, 3H), 0.76 and 0.72 (s, 3H, TiMe) ppm.

¹³ C {1H} NMR (C6D6): 160.13,159.86,141.33,140.46,138.39,137.67,136.74,134.83,131.48,129.90,129.78,127.69,127.65,127.60,127.45,126.87,126.81,121. 120.15, 119.15, 118.93, 114.77, 111.60, 57.54, 55.55, 55.23, 51.73, 50.43, 50.36, 27.83, 27.67, 22.37, 22.31, 20.53, 20.26, 14.29, 13.51, 13.42, 13.06, 12.80 ppm.

[Synthesis Example 10] Synthesis of titanium compound 13 < Catalyst 5 >

Was synthesized in the same manner as in the synthesis of the compound 9 of the above Synthesis Example 6, except that the compound 8 prepared in Synthesis Example 5 was used instead of the above-mentioned Compound 4. The yield was 57%. Was obtained as a mixture of 1: 0.8 ratio by the direction of the thiophene ring and the direction of the methyl group attached to the tetrahydroquinoline.

^{1 H NMR (C6D6): δ} 7.12 and 7.09 (d, J = 7.2 Hz, 1H), 6.96 and 6.94 (d, J = 7.2 Hz, 1H), 6.82 and 6.80 (t, J = 7.2 Hz, 1H), 1H), 6.44 (d, J = 7.2 Hz, 1H), 6.47 and 6.46 (d, 2H, CH2), 1.20 and 1.18 (d, 3H), 2.18 (s, 3H), 2.18 , J = 7.2 Hz, 3H), 0.77 and 0.71 (s, 3H, TiMe), 0.49 and 0.40 (s, 3H, TiMe) ppm.

¹³ C {1H} NMR (C6D6): 159.83, 159.52, 145.93, 144.90, 140.78,139.93,139.21,138.86,135.26,131.56,129.69,129.57,127.50,127.46,127.38,127.24,121.29,121.16,120.05,119.96, 118.90, 118.74, 117.99, 117.74, 113.87, 110.38, 57.91, 55.31, 54.87, 51.68, 50.27, 50.12, 34.77, 27.58, 27.27, 23.10, 22.05, 20.31, 19.90, 16.66, 14.70, 13.11, 12.98, 12.68 ppm.

[Synthesis Example 11] Synthesis of dichlorotitanium compound 14 < Catalyst 6 >

Compound 14 was synthesized according to Reaction Scheme 1 below.

<Reaction Scheme 1>

Methyl lithium (1.63 g, 3.55 mmol, 1.6 M diethyl ether solution) was added dropwise at -30 째 C to a diethyl ether solution (10 mL) in which Compound 7 (0.58 g, 1.79 mmol) was dissolved. The solution was stirred overnight at room temperature, then cooled to -30 ° C and then Ti (NMe ₂ ) ₂ Cl ₂ (0.37 g, 1.79 mmol) was added in one portion. The solution was stirred for 3 hours and then all the solvent was removed using a vacuum pump. The resulting solid was dissolved in toluene (8 mL), followed by Me ₂ SiCl ₂ (1.16 g, 8.96 mmol). The solution was stirred at 80 ° C for 3 days and then the solvent was removed using a vacuum pump. A red solid compound was obtained (0.59 g, 75%). ^{The 1} H NMR spectrum confirmed the presence of 2: 1 of the two stereochemically active compounds.

^{1 H NMR (C6D6): δ} 7.10 (t, J = 4.4 Hz, 1H), 6.90 (d, J = 4.4 Hz, 2H), 5.27 and 5.22 (m, 1H, NCH), 2.54-2.38 (m, 1H 3H), 1.94 and 1.93 (s, 3H), 1.89 and 1.84 (s, 3H), 2.03 (s, , 1.72-1.58 (m, 2H, CH 2), 1.36-1.28 (m, 2H, CH 2), 1.17 and 1.14 (d, J = 6.4, 3H, CH 3) ppm.

¹³ C {1H} NMR (C6D6): 162.78, 147.91, 142.45, 142.03, 136.91,131.12,131.70,131.10,128.90,127.17,123.39,121.33,119.87,54.18,26.48,21.74,17.28,14.46,14.28,13.80, 13.27 ppm.

[Reference Example]

All the polymerization was carried out in a high pressure autoclave completely blocked with outside air, and the required amount of solvent, co-catalyst, monomers to be polymerized were injected into the high-pressure reactor, and the catalyst was put into the reactor.

MAO (methylaluminoxane) was purchased from Albemarle Corporation using 10% toluene solution (PMAO-10%). Catalyst of bisindenylzirconium dichloride (Ind ₂ ZrCl ₂ ) and racemic ethylene bisindenyl zirconium dichloride, rac-C ₂ H ₄ (Ind) ₂ ZrCl ₂ Were purchased from Strem and used without further purification.

The molecular weight and molecular weight distribution of the resulting polymer were measured by GPC (Gel Permeation Chromatography, PL-GPC220) method. The melting point and glass transition temperature were measured by DSC (Differential Scanning Calorimetry, TA Instruments). The stereoregularity diagram of polypropylene (Isotacticity, mmmm Pentad II) was obtained by dissolving polypropylene in trichlorobenzene and benzene-d6 (C6D6) and then carrying out 13C NMR (Bruker, Avance 400 Spectrometer).

[Manufacturing Example 1] Polymerization of Atactic Polypropylene (aPP)

The inside of a stainless steel autoclave having an internal capacity of 2 L at room temperature was completely replaced with nitrogen. 4.0 mL (6 mmol) of methylaluminoxane toluene solution was added at room temperature while nitrogen purging was maintained. Then, 500 g of propylene was added and the temperature was raised to 70 ° C. Then, the compound 14 Was dissolved in toluene (1.5 mL, 3.0 μmol of Ti). Thereafter, polymerization was carried out for 1 hour. After completion of polymerization, the mixture was kept at room temperature, and excess propylene was removed through an exhaust line to obtain a polymer. The obtained polymer was dried for 4 hours or more while heating at 80 占 폚 using a vacuum oven to finally obtain polypropylene. The physical properties of the prepared atactic polypropylene (aPP) are shown in Table 2 below.

polymerization
Synthetic example activation
(Kg / mmol of Ti · hr) Molecular weight (Mw)
(× 10 ^-3 ) Molecular weight distribution (MwD, Mw / Mn) Melting point
(° C) II
(%, mmmm) density
(g / mL) Polypropylene
polymerization 46.0 349 5.25 none 9.6 0.850

As can be seen from Table 2, it was confirmed that when propylene was homopolymerized using the catalyst system according to the present invention, atactic polypropylene (aPP) having no melting point and high molecular weight could be produced.

In addition, the atactic polypropylene polymerized in the above-mentioned Production Example 1 was a polypropylene-based material such as homopolypropylene, and it was confirmed that the kneading was good and the dispersion of the atactic polypropylene in the homopolypropylene was easy. When a certain amount of the atactic polypropylene was added, whitening of the homopolypropylene was reduced, and the polypropylene specimen was not bent even when bent. In addition, whitening of homopolypropylene is reduced when a suitable amount of atactic polypropylene is added, but it may affect the inherent properties of homopolypropylene.

&Lt; Example 1: Polypropylene resin composition and production of molded article using the same &

The temperature of the brabender was set at 180 DEG C to reach the temperature. After the speed was changed to 100 rpm, 49 g of homopolypropylene; 0.1 g of a phenolic antioxidant (SONGNOX 1076), 0.1 g of a phosphite antioxidant (Songnox 1680), 0.2 g of a nucleating agent (Mitsui Toatsu NC-4), a neutralizer (SONGSTAB SC-110) was added to the brabender. Then, the product was taken out of the mold for 5 minutes and then taken out. The product was placed in a 2-T molder and compressed in a press machine set at 200 ° C. for 5 minutes to form a final product of Example 1 in which the properties were measured. At this time, the finished product was made into a plate-shaped molded article having a size of 100 mm × 100 mm × 2 mm.

&Lt; Example 2 >

Except that 48 g of homopolypropylene and 1.5 g of atactic polypropylene polymerized with a metallocene system were added to the molded product of Example 2. The molded product of Example 2 was produced in the same manner as in Example 1,

&Lt; Example 3 >

Except that 47 g of homopolypropylene and 2.5 g of atactic polypropylene polymerized with a metallocene system were added, and the molded article of Example 3 was produced in the same manner as in Example 1.

&Lt; Comparative Example 1 &

The temperature of the brabender was set at 180 DEG C to reach the temperature. 49.5 g of homopolypropylene (product name: SJ-170T) without treatment with atactic polypropylene, 0.1 g of a phenolic antioxidant (SONGNOX 1076), 0.1 g of a phosphite antioxidant (Songnox 1680) , 0.2 g of nucleating agent (Mitsui Toatsu NC-4) and 0.1 g of neutralizing agent (SONGSTAB ™ SC-110) were added to the brabender. Then, the product was taken out of the mold after mixing for 5 minutes. The product was placed in a 2-T molder and pressed in a press machine set at 200 ° C for 5 minutes to form a final product of Comparative Example 1 in which the properties were measured. At this time, the final product was made into a plate of 100 mm × 100 mm × 2 mm in width, height and height.

&Lt; Comparative Example 2 &

The temperature of the brabender was set at 180 DEG C to reach the temperature. After the speed was changed to 100 rpm, a mixture of 47 g of homopolypropylene, 2.5 g of ethylene-octene copolymer (Engage 8842), 0.1 g of phenolic antioxidant (SONGNOX 1076), 0.1 g of phosphite antioxidant (Songnox 1680) 0.2 g of Mitsui Toatsu NC-4) and 0.1 g of neutralizer (SONGSTAB ™ SC-110) were added to the brabender. The following procedure was carried out in the same manner as in Comparative Example 1.

&Lt; Comparative Example 3 &

The temperature of the brabender was set at 180 DEG C to reach the temperature. After the speed was changed to 100 rpm, a mixture of 47 g of homopolypropylene, 2.5 g of a styrene-based elastomer (product name: KRATON G-1650), 0.1 g of a phenolic antioxidant (SONGNOX 1076), 0.1 g of a phosphite antioxidant (Songnox 1680) 0.2 g of a nucleating agent (Mitsui Toatsu NC-4) and 0.1 g of a neutralizing agent (SONGSTAB ™ SC-110) were added to the brabender. The following procedure was carried out in the same manner as in Comparative Example 1.

[Experimental Example 1] Evaluation of Whiteness of Polypropylene Resin Molded Articles

The whitening resistance of the polypropylene resin molded articles produced in Examples 1 to 3 and Comparative Examples 1 to 3 was evaluated as follows.

More specifically, in Examples 1 to 3, atactic polypropylene (aPP) polymerized by using a metallocene-based catalyst in homopolypropylene was blended according to the composition shown in the following Table 3, and then the blended polypropylene resin composition was used To thereby produce a plate-shaped molded article having a size of 100 mm x 100 mm x 2 mm. In Comparative Examples 1 to 3, homopolypropylene product (product name: SJ-170T) without treatment with atactic polypropylene, ethylene-octene copolymer (product name: Engage 8842) and styrene-based elastomer (trade name: KRATON &Lt; / RTI &gt; G-1650).

In order to improve the accuracy and reliability, the whitening resistance of the molded product was divided into two types. In the first method, 5 kg of weight (25 mm in diameter) was dropped from a height of 100 cm on the molded article, and the haze of the incidence of bleaching point bleeding was measured and recorded. The second measurement method was to measure the degree of whitening of the specimen at the center of the specimen when the specimen was bent 180 degrees so that the face and the face could touch. The haze measured by the two methods was measured using the NDH-5000 Hazemeter, a dedicated measuring device. The results are shown in Table 3 below.

For reference, the addition of atactic polypropylene to homopolypropylene may adversely affect the inherent physical properties of the homopolypropylene, so the addition of atactic polypropylene to the homopolypropylene results in the occurrence of whitening Were compared as follows.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 A content
(weight %) 98 96 94 99 94 94 B content
(weight %) One 3 5 0 0 0 C content
(weight %) 0 0 0 0 5 0 D content
(weight %) 0 0 0 0 0 5 Other additives
(weight %) One One One One One One Basic Specimen
Haze (%) 47 46 46 48 48 49 HAZE 1
(%) 63 52 49 88 69 73 HAZE 2
(%) 78 55 50 95 78 72 A: Homopolypropylene (SJ-170T)
B: Atactic polypropylene polymerized in a metallocene system
C: Ethylene-octene copolymer (Engage 8842)
D: styrene-based elastomer (KRATON (TM) G-1650)
HAZE 1: HAZE measurement of molded parts by impact of impact
HAZE 2: HAZE measurement of molded parts due to bending damage

As a result of the experiment, Haze confirmed that the whitening resistance of the homopolypropylene was improved by controlling the addition amount of atactic polypropylene (see Table 3).

More specifically, the molded articles of Examples 1 to 3 all had lower haze values than those of Comparative Example 1 which did not contain atactic polypropylene. Particularly, in Examples 2 to 3, haze it was confirmed that the haze value was remarkably low. Particularly, in Example 2, it was confirmed that the whitening resistance was excellent due to the content of atactic polypropylene. It was confirmed that the content of atactic polypropylene was lower than that of styrene-based elastomer, And the effect of inner whitening was excellent.

[Experimental Example 2] Evaluation of impact resistance of a polypropylene resin molded article

The impact resistance of the polypropylene resin molded articles produced in Examples 1 to 3 and Comparative Example 1 was evaluated as follows.

More specifically, each of the molded articles prepared by compounding homopolypropylene with atactic polypropylene by weight was used to measure the impact resistance properties of the following Table 4, and by using atactic polypropylene, homopolypropylene It was possible to confirm how it affected the change of physical properties.

For reference, many methods are standardized in the impact test, and numerical values by Izod method and Charpy method are most commonly used. In this experiment, the Izod impact strength test method (ASTM D-256) was used. More specifically, the Izod impact strength was measured as follows. The impact energy was obtained by dividing the absorbed energy obtained at the rotating height by the weight of the specimen using a pendulum of a certain weight divided by the cross - sectional area of the specimen notch.

The flexural test is performed by placing the specimen on two points separated by a certain distance and measuring the stress and distortion by pressing the specimen in a vertical direction with a constant speed until the specimen breaks. In this test, the bending elastic modulus (ASTM D790), which is the value obtained by dividing the force exerted from the top of the specimen by the deformation of the specimen, was measured through the flexural test.

The flowability was measured by the melt index and measured under a load of 2.16 kg at 230 캜 according to ASTM D1238.

Example 1 Example 2 Example 3 Comparative Example 1 A content
(weight%) 98 96 94 99 B content
(weight%) One 3 5 0 Other additives
(weight %) One One One One Impact strength
(kgf · cm / cm) 2.7 3.8 5.2 2.0 Flexural modulus
(kgf / cm2) 14,700 14,500 14,000 15,200 Heat deformation temperature (캜) 99.7 99.5 99.8 100 Flowability (g / 10 min) 28 27 27 28 A: Homopolypropylene (SJ-170T)
B: Atactic polypropylene polymerized in a metallocene system

As a result of the experiment, when the atactic polypropylene (aPP) was added in an amount of 3% by weight or less as in Examples 1 and 2, the impact strength of the molded article was increased and the flexural modulus was slightly decreased, but the impact strength and flexural modulus Respectively. When atactic polypropylene was added in an amount of 5 wt% or more, the variation of impact strength and flexural modulus increased. On the other hand, it was confirmed that the heat distortion temperature and the fluidity were not largely changed as a whole (see Table 4).

From the above-mentioned results, it was confirmed that the addition of atactic polypropylene within 3% by weight can increase the whitening resistance while maintaining the inherent physical properties of the crystalline polypropylene.

In the present invention, the results of the above Tables 3 to 4 indicate that when a minimum amount of atactic polypropylene is added, the physical properties of the resin itself are favorably affected and excellent physical properties are obtained.

That is, the whitening resistance of the crystalline polypropylene was improved when the atactic polypropylene was added, and in particular, when the content of the atactic polypropylene was 3 wt% or less, the impact strength and flexural modulus of the crystalline polypropylene were maintained, Was increased . It is expected that it can be usefully used for various polypropylene resins by suggesting measures to improve the whitening resistance while maintaining or increasing the inherent property of the crystalline polypropylene that has been commercialized in the past.

Claims (11)

(a) 50 to 99% by weight of polypropylene (excluding atactic polypropylene);
(b) 0.1 to 10% by weight of atactic polypropylene; And
(c) 0.1 to 49.9% by weight of at least one additive,
And a polypropylene resin composition. The method according to claim 1,
The polypropylene (a) is a propylene homopolymer; Wherein the polypropylene resin composition is a random copolymer, block copolymer or graft copolymer of propylene and at least one or more olefin monomers. The method according to claim 1,
Wherein the polypropylene (a) is crystalline homopolypropylene. The method according to claim 1,
Wherein the atactic polypropylene (b) satisfies the following conditions (i) to (iv):
(i) a stereoregularity (isotacticity, pentad II, mmmm) of 5 to 20%
(ii) a molecular weight distribution (Mw / Mn) ranging from 1 to 10,
(iii) a weight average molecular weight (Mw) in the range of 10,000 to 1,000,000,
(iv) a density of 0.8 to 0.9 g / ml. The method according to claim 1,
Wherein the atactic polypropylene (b) is prepared by polymerizing propylene in the presence of a transition metal catalyst represented by the following formula (1): &lt; EMI ID =
[Chemical Formula 1]

In Formula 1,
M is a transition metal selected from the group consisting of Group 4 elements on the periodic table;
Q ¹ and Q ² are the same or different and are each halogen, (C ₁ -C ₂₀₎ alkyl, (C ₂ -C ₂₀₎ alkenyl, (C ₂ -C ₂₀₎ alkynyl, independently, (C ₆ -C ₂₀₎ aryl, (C ₁ -C ₂₀₎ alkyl (C ₆ -C ₂₀₎ aryl, (C ₆ -C ₂₀₎ aryl (C ₁ -C ₂₀₎ alkyl, (C ₁ -C ₂₀₎ alkyl amido , (C ₆ -C ₂₀ ) arylamido, and (C ₁ -C ₂₀ ) alkylidene;
R ¹ to R ¹⁰ are the same as or different from each other, and each independently hydrogen; (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Acetal, which does not include or include a ketal or ether (C ₂ -C ₂₀₎ alkenyl; (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl, with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Or (C ₁ -C ₂₀ ) silyl, with or without an acetal, ketal or ether group; In this case, R ¹ and R ² , or R ³ and R ⁴ may be connected to each other to form a ring, and two or more of R ⁵ to R ¹⁰ may be connected to each other to form a ring;
R ¹¹ to R ¹³ are the same as or different from each other, and each independently hydrogen; (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; Acetal, which does not include or include a ketal or ether (C ₂ -C ₂₀₎ alkenyl; (C ₁ -C ₂₀ ) alkyl (C ₆ -C ₂₀ ) aryl, with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl, with or without an acetal, ketal or ether group; (C ₁ -C ₂₀ ) silyl with or without an acetal, ketal or ether group; (C ₁ -C ₂₀₎ alkoxy; And (C ₆ -C ₂₀₎ is selected from the group consisting of aryloxy; Wherein R &lt; ¹¹ &gt; and R &lt; ¹² & Or R ¹² and R ¹³ may be connected to each other to form a ring. 6. The method of claim 5,
M is titanium (Ti), zirconium (Zr) or hafnium (Hf);
Q ¹ and Q ² are the same or different and are each independently methyl or chlorine,
R ¹ to R ⁵ are the same or different and are each independently hydrogen or methyl,
And R ⁶ to R ¹³ are each independently hydrogen. 6. The method of claim 5,
Wherein the catalyst further comprises at least one promoter compound selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 4:
(2)
^{- [Al (R 21) -O} ] a -
(3)
D ( ^R31 ) 3
[Chemical Formula 4]
^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -
In the above Chemical Formulas 2 to 4,
R &lt; ²¹ &gt; are each independently a halogen radical; (C ₁ -C ₂₀ ) hydrocarbyl radical; Or a (C ₁ -C ₂₀ ) hydrocarbyl radical substituted with halogen; a is an integer of 2 or more;
D is aluminum or boron;
R ³¹ are each independently a halogen radical; (C ₁ -C ₂₀ ) hydrocarbyl radical; Or a (C ₁ -C ₂₀ ) hydrocarbyl radical substituted with halogen;
L is a neutral or cationic Lewis acid;
Z is an element selected from the group consisting of Group 13 elements on the periodic table;
A are each independently substituted by 1 or more hydrogen atoms are halogen, (C ₁ -C ₂₀₎ hydrocarbyl, (C ₁ -C ₂₀₎ alkoxy, or (C ₆ -C ₂₀₎ aryloxy radical, (C ₆ - C ₂₀₎ aryl or (C ₁ -C ₂₀₎ alkyl radical. 8. The method of claim 7,
Wherein the use ratio of the transition metal catalyst compound of Formula 1 and the co-catalyst compound is in the range of 1: 1 to 20,000 molar ratio. The method according to claim 1,
The additive (c) is selected from the group consisting of a nucleating agent, a coloring agent, an MI synergist, an antioxidant, a catalyst neutralizing agent, a pigment, a dispersant, a lubricant, an antistatic agent, a UV stabilizer, a slip agent, an anti- Polypropylene resin composition. A molded article characterized by being produced from the polypropylene resin composition according to any one of claims 1 to 9. 11. The method of claim 10,
Wherein the molded article is a refrigerated container, a freezing container, a multipurpose container, an automobile interior and exterior material, a food packaging container, a bottle cap, a packaging film, a protective film, a decor sheet, a retort pouch, a medicine container or an input /