KR20170114064A - Preparing method for high melt strength polypropylene resin composition - Google Patents

Abstract

Disclosed is a method for producing a hyperbranched polypropylene resin having improved melt tension by controlling the polymer structure of a diene-modified polypropylene through a process simplification using a metallocene catalyst system. The present invention relates to a process for producing a propylene homopolymer having a branching index of not more than 0.95, a graft density of not less than 0.005, a gel content of not more than 5 wt% and a melt tension (ARES (Advanced Rheometric Expansion System) Melt Strength) of 5 g or more.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a high melt tension polypropylene resin,

The present invention relates to a process for producing a high melt strength polypropylene resin, and more particularly, to a process for producing a high melt strength polypropylene resin using a metallocene catalyst.

Polypropylene (PP) has a high melting point and a low density. In addition, excellent chemical resistance and high tensile modulus can be obtained at low cost. For this reason, it boasts an overwhelming market share of plastic products. However, in the process where the tension stiffness is mainly required, the process characteristic is insufficient. In order for polypropylene to be used in shaping processes such as foaming, thermoforming, extrusion coating, blow molding, etc., it is necessary to strain hardening (manifestation of high melt tension) of the melt. In order to improve this, modification of polypropylene is essential . In that way, a broader (including bimodal) molecular weight distribution (MWD) is a way to improve this phenomenon, but rather than adding a long side branch (LCB) to the polypropylene backbone to efficiently increase the melt tension to be.

Korean Patent Publication No. 2011-0084303 discloses a method for producing long chain-branched isotactic polypropylene after preparation of oligomer polypropylene and a method using two kinds of catalysts, oligomer catalyst and crosslinking catalyst, There is an uneconomical problem in terms of facilities and manufacturing costs.

US Patent Nos. 5,368,919, 5,414,027, 5,541,236, 5,554,668, 5,591,785 and 5,731,362 disclose polypropylene polymers having a high melt tension. Although the performance of the polypropylene polymer according to this patent is excellent, there is a problem that the manufacturing cost of the electron beam irradiation equipment is high and the productivity is low, and thus the manufacturing cost of the high melt tension polypropylene is high.

U.S. Pat. Nos. 5,416,169, 4,525,257, and WO 97/049759 disclose a method for introducing long chains into polypropylene by reacting organic peroxides with polypropylene under specific reaction conditions, There is a problem that the production time is long and the productivity is low or the reaction extrusion process must be carried out because the reaction conditions are made stepwise in proportion, and the polypropylene is decomposed by the peroxide.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and it is an object of the present invention to provide a hyperbranched polypropylene resin having improved melt tension by controlling the polymer structure of a diene-modified polypropylene through a process simplification using a metallocene catalyst system I want to give you a way.

In order to solve the above problems, the present invention provides a process for producing a metallocene catalyst, which comprises contacting a propylene and a diene compound directly with a metallocene catalyst to obtain a catalyst having a branching index of 0.95 or less, a graft density of 0.005 or more, % Or less and a melt tension (ARES (Melt Strength) of Advanced Rheometric Expansion) of 5 g or more.

And the diene compound is at least one selected from the group consisting of aliphatic dienes and aromatic dienes having 4 to 20 carbon atoms.

The diene compound may be at least one selected from the group consisting of 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, Dodecadienes, 1,12-tridecadienes, 1,13-tetradecadienes, and the like.

In the polypropylene resin, the diene compound is contained in an amount of 0.001 to 4 mol%.

And the polypropylene resin is a non-monomodal polypropylene resin having a molecular weight distribution of 3.0 or more.

And the polypropylene resin has a flow flow index (MFR) of 0.1 to 100 g / 10 min.

Further, the polypropylene resin has a melting peak of 160 DEG C or less.

And the metallocene catalyst comprises a transition metal compound represented by the following general formula (1).

[Chemical Formula 1]

M is 2 and n is 0 and M is 0 and n is 1 when M is a divalent transition metal of Group 4 in the periodic table; is M and η ⁵ - is a cyclopentadienyl ring which can be combined, wherein the cyclopentadienyl ring (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl, tri (C1- (C6-C20) arylsilyl, (C6-C20) arylsilyl, (C1-C20) alkyldi It can be further substituted with one or more selected from the group consisting of alkenyl and; D is SiR ³ R ⁴ or (C2-C20) alkenylene; R ³ and R ⁴ are each independently hydrogen, (C1-C20) alkyl, (C3-C20) or cycloalkyl, or (C6-C20) aryl, wherein R ³ and R ⁴ are (C4-C7) are connected by an alkylene to form a ring, and; R ¹ is (C1-C20) alkyl ; Ar is (C6-C20) aryl; R ² is hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl or (C6- C20) aryl; wherein Ar and R ² are (C1-C7) alkylene, (C2-C7) alkenylene or a (C4-C7) are connected to the alkane diethoxy alkenylene may form a fused ring; X ¹ is a halogen , (C1-C20) alkyl, (C1-C20) alkoxy, (C3-C20) cycloalkyl, (C6-C20) aryl, (C6-C20) ^{aryloxy, -OSiR a R b R c,} -SR d, -NR ^e R ^f or R ^h and -PR ^g; R ^a to R ^h are each independently (C1-C20) alkyl, (C6-C20) aryl or (C3-C20) cycloalkyl; X ² is a neutral conjugated or non-conjugated (C4-C20) diene, and; wherein the R ¹ alkyl, an Ar aryl, R ^2, R ³ and R ⁴ for alkyl, cycloalkyl, aryl are independently from each other are selected from halogen, (C1-C20) alkyl, Which may be further substituted with one or more substituents selected from the group consisting of halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy and have.)

The polypropylene resin manufacturing method according to the present invention is carried out by directly contacting propylene and a diene compound using a metallocene catalyst, so that compared with a conventional high-melt-strength polypropylene manufacturing method such as a two-step reaction or a reaction extrusion method, This is inexpensive and economical.

Also, it is possible to control the long side-chain structure such as the branching of the internal chain of the polypropylene and the molecular weight in comparison with the reaction using the existing peroxide, and thus a polypropylene resin having excellent physical properties can be provided.

1 is a graph showing a molecular weight distribution curve obtained by gel chromatography of a polypropylene resin produced according to Example 1 of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Throughout the specification, when an element is referred to as "including " an element, it means that it can include other elements, not excluding other elements, unless specifically stated otherwise.

The present invention relates to a process for producing a propylene homopolymer having a branching index of not more than 0.95, a graft density of not less than 0.005, a gel content of not more than 5 wt% and a melt tension (ARES (Advanced Rheometric Expansion System) Melt Strength) of 5 g or more.

According to the present invention, by directly contacting propylene and a diene compound using a metallocene catalyst, it is possible to produce a polypropylene resin having a branched structure and improved melt tension compared to a polypropylene resin polymerized under similar conditions. This makes it possible to control the diene content, branch structure density, molecular weight and the like in the polypropylene, thereby improving the melt tension and suppressing the gel formation, thereby satisfying the required physical properties sufficiently.

According to one embodiment of the present invention, the copolymer produced through the polymerization process which is carried out by directly contacting propylene and the diene compound is relatively insoluble and / or rigid so that the polymer chain is rapidly immobilized according to this information ≪ / RTI > by slurry or bulk polymerization of propylene and diene. Such immobilisation can be carried out, for example, by using a solid insoluble catalyst and by performing copolymerization in a medium in which the resulting copolymer is generally insoluble and keeping the polymerization reactants and products below the crystalline melting point of the copolymer.

The metallocene catalyst composition described later is preferable for copolymerization of diene and propylene. Suitable polymerization processes for the copolymerization of propylene are well known to those skilled in the art and include bulk polymerization, solution polymerization, slurry polymerization and low pressure gas phase polymerization. The metallocene catalyst compositions are particularly useful in known operating forms employing fixed bed, moving bed or slurry processes carried out in single, series or parallel reactors.

According to one embodiment of the present invention, any of the above polymerization processes may be used. Typical propylene polymerization processes use a slurry process in which the polymerization medium may be a liquid monomer such as propylene or a hydrocarbon solvent or diluent, preferably an aliphatic paraffin such as propane, isobutane, hexane, heptane, cyclohexane, or an aromatic diluent such as toluene . In this case, the polymerization temperature may be in any range between 40 and 100 캜. The pressure can be between 5 and 50 bar.

A method for producing a polypropylene resin according to the present invention includes: a transition metal compound represented by the following formula (1); And at least one promoter compound selected from the group consisting of boron compounds represented by the following formulas (2) to (4) and aluminum compounds represented by the following formulas (5) to (9) And then polymerizing the compound.

[Chemical Formula 1]

M is 2 and n is 0 when M is a tetravalent transition metal of Group 4 on the periodic table and m is 0 and n is 1 when M is a divalent transition metal of Group 4 on the periodic table; Cp is a cyclopentadienyl ring which may be bound to M by η ⁵ - and the cyclopentadienyl ring is optionally substituted with one or more substituents selected from the group consisting of (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 6 -C 20) (C6-C20) alkylsilyl, tri (C6-C20) arylsilyl, (C1-C20) alkyldi ≪ / RTI >alkenyl; D is SiR ³ R ⁴ or (C2-C20) alkenylene; R ³ and R ⁴ are each independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl or (C6-C20) aryl, wherein R ³ and R ⁴ are connected to the (C4-C7) alkylene To form a ring; R < ¹ > is (C1-C20) alkyl; Ar is (C6-C20) aryl; R ² is hydrogen, (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl or (C 6 -C 20) aryl; Ar and R ² may be linked by (C 1 -C 7) alkylene, (C ² -C 7) alkenylene or (C 4 -C 7) alkane dienylene to form a fused ring; X ¹ is halogen, (C1-C20) alkyl, (C1-C20) alkoxy, (C3-C20) cycloalkyl, (C6-C20) aryl, (C6-C20) aryloxy, -OSiR ^a R ^b R ^c, -SR ^d , -NR ^e R ^f or -PR ^g R ^h ; R ^a to R ^h are, independently of each other, (C 1 -C 20) alkyl, (C 6 -C 20) aryl or (C 3 -C 20) cycloalkyl; X ² is a neutral, conjugated or nonconjugated (C4-C20) diene; Alkyl, Ar of the R ¹ aryl, R ^2, R ³ and the R ⁴ alkyl, cycloalkyl, aryl are independently from each other are selected from halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C3-C20 ) Cycloalkyl, (C6-C20) aryl, (C1-C20) alkoxy and (C6-C20) aryloxy.

(2)

B (R ¹¹ ) ₃

(3)

[R ₁₂ ] ⁺ [B (R ¹¹ ) ₄ ] ^-

[Chemical Formula 4]

_{^{[(R 13) r ZH]}} + [B (R 11) 4] -

In formulas (2) to (4), B is a boron atom; (C1-C20) alkyl substituted by a fluorine atom, (C1-C20) alkoxy substituted by a fluorine atom, and (C1-C20) ≪ / RTI > R ¹² is a (C5-C7) aromatic radical or a (C1-C20) alkyl (C6-C20) aryl radical or a (C6-C20) arylC1-C20) alkyl radical; Z is a nitrogen or phosphorus atom; R ¹³ is an (Cl-C20) alkyl radical or an Anilinium radical substituted with two (C1-C10) alkyls together with the nitrogen atom; r is an integer of 2 or 3;

[Chemical Formula 5]

- [Al (R14) -O] _s-

[Chemical Formula 6]

(R ¹⁴ ) ₂ Al- [O (R ¹⁴ )] _t - (R ¹⁴ ) ₂

(7)

(R15) uAl (E) 3-u

[Chemical Formula 8]

(R ¹⁶ ) ² AlOR ¹⁷

[Chemical Formula 9]

R ^{16 is} Al (OR ¹⁷ ) ₂

In formulas (5) to (9), R14 is (C1-C20) alkyl; s and t are each independently an integer of 5 to 20; R ¹⁵ and R ¹⁶ are each independently (C 1 -C 20) alkyl; E is a hydrogen atom, a halogen atom or (C1-C20) alkyl; u is an integer from 1 to 3; R < ¹⁷ > is (C1-C20) alkyl or (C6-C20) aryl.

The term " alkyl " as used herein refers to a monovalent straight or branched saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms. Examples of such alkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Butyl, pentyl, hexyl, octyl, dodecyl, and the like.

The term " cycloalkyl " as used in the present invention means a monovalent alicyclic alkyl radical consisting of one ring, examples of which include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, But are not limited to, cyclononyl, cyclodecyl, and the like.

The term " alkenyl " as used herein also refers to straight or branched chain hydrocarbon radicals containing one or more carbon-carbon double bonds, including ethenyl, propenyl, butenyl, pentenyl and the like, But is not limited to.

The term " aryl ", as defined in the present invention, is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, including a single or fused ring system. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl, triphenylenyl, pyreneyl, perylenyle, klycenyl, naphthacenyl, fluoranthenyl and the like.

The term " alkoxy " as used in the present invention means an -O-alkyl radical where 'alkyl' is as defined above. Examples of such alkoxy radicals include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy and the like.

The term " aryloxy " as used in the present invention means an -O-aryl radical, wherein 'aryl' is as defined above. Examples of such aryloxy radicals include, but are not limited to, phenoxy, biphenoxy, naphthoxy, and the like.

The term " halogen " as used in the present invention means a fluorine, chlorine, bromine or iodine atom.

In the present invention, the transition metal compound is a cyclopentadiene derivative ligand connected with a bridge group of silicon or alkenylene and an anisole derivative ligand in which the aryl is substituted at the 4-position, And has an ansa-metallocene structure.

As described above, the transition metal compound has an indene derivative ligand in which the aryl is substituted at the 4-position, so that it has higher catalytic activity and higher copolymerization activity than the transition metal compound having an aryl group-unsubstituted ligand at the 4-position of indene This makes it possible to produce a polypropylene resin capable of controlling the melt tension and molecular weight, the uniform composition distribution and the long side structure control.

In one embodiment of the present invention, the transition metal compound represented by the general formula (1) is more preferably represented by the following general formula (10) or (11).

[Chemical formula 10]

(11)

In Chemical Formulas 10 and 11, M ¹ is a tetravalent Group 4 transition metal, M ² is a divalent Group 4 transition metal, and Cp, Ar, R ¹ to R ⁴ , X ¹ and X ² are as defined in claim 1 It is the same as the definition.

In one embodiment of the present invention, m is 2 and n is 0 when M is tetravalent titanium, zirconium or hafnium, m is 0 when M is divalent titanium, zirconium or hafnium, and n is 1; Cp is a cyclopentadienyl ring in which (C1-C20) alkyl is substituted or unsubstituted; R ¹ is (C ¹ -C 20) alkyl, (C 6 -C 20) aryl (C 1 -C 20) alkyl or halo (C 1 -C 20) alkyl; Ar is (C6-C20) aryl; R ² is hydrogen or (C 6 -C 20) aryl; Ar and R ² may be linked to form a fused ring with (C 1 -C 7) alkylene, (C ² -C 7) alkenylene or (C 4 -C 7) alkane dienylene, and the aryl of Ar and R ² may be halogen (C6-C60) aryloxy, (C6-C60) aryloxy, (C6-C60) aryloxy, Lt; / RTI > may be further substituted with a substituent; R ³ and R ⁴ are independently selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl (C 1 -C 20) alkyl, halo (C 1 -C 20) C20) aryl, R < ³ > and R < ⁴ > may be linked by (C4-C7) alkylene to form a ring; X ¹ is halogen, (C ¹ -C 20) alkyl, (C 1 -C 20) alkoxy or di (C 1 -C 20) alkylamino; X ² can be a neutral conjugated 1,3- (C4-C20) diene.

In one embodiment of the present invention, in formulas (10) and (11), M ¹ is tetravalent titanium, zirconium or hafnium; M ² is divalent titanium, zirconium or hafnium; Cp is a cyclopentadienyl ring in which (C1-C20) alkyl is substituted or unsubstituted; R ¹ is (C ¹ -C 20) alkyl, (C 6 -C 20) aryl (C 1 -C 20) alkyl or halo (C 1 -C 20) alkyl; Ar is (C6-C20) aryl; R ² is hydrogen or (C 6 -C 20) aryl; Ar and R ² may be linked to form a fused ring with (C 1 -C 7) alkylene, (C ² -C 7) alkenylene or (C 4 -C 7) alkane dienylene, and the aryl of Ar and R ² may be halogen (C6-C60) aryloxy, (C6-C60) aryloxy, (C6-C60) aryloxy, Lt; / RTI > may be further substituted with a substituent; R ³ and R ⁴ are independently selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl (C 1 -C 20) alkyl, halo (C 1 -C 20) C20) aryl, R < ³ > and R < ⁴ > may be linked by (C4-C7) alkylene to form a ring; X ¹ is halogen, (C ¹ -C 20) alkyl, (C 1 -C 20) alkoxy or di (C 1 -C 20) alkylamino; X ² can be a neutral conjugated 1,3- (C4-C20) diene.

In one embodiment of the present invention, the Cp is cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl or butylcyclopentadienyl; R ¹ is methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl or trifluoromethyl; Ar is phenyl, naphthyl, biphenyl or anthryl; R ² is hydrogen, phenyl, naphthyl, biphenyl or anthryl; The phenyl, naphthyl, biphenyl or anthryl of Ar and R ² is optionally substituted with one or more substituents selected from the group consisting of fluoro, chloro, iodo, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, trifluoromethyl, cyclopropyl, Which may be further substituted with one or more substituents selected from the group consisting of alkyl, cyclohexyl, phenyl, naphthyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and phenoxy; Wherein Ar and R ² may be connected to each other by methylene, ethenylene or 1,3-butane dienylene to form a fused ring, and R ³ and R ⁴ may be the same or different and are each a methyl, ethyl, propyl, butyl, pentyl, hexyl, Fluoromethyl, phenyl, naphthyl, biphenyl, anthryl or tolyl, and R ³ and R ⁴ may be linked together with a butylene or pentylene to form a ring; X ¹ is selected from the group consisting of fluoro, chloro, iodo, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, Amino, dipropylamino, dibutylamino, butylpropylamino, dihexylamino, dioctylamino or methylethylamino; X ² can be 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene or 1,3-octadiene.

In one embodiment of the present invention, the transition metal compound may be selected from compounds having the following structures, but is not limited thereto.

In the above structure, Cp is cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, diisopropylcyclopentadienyl, trimethylcyclopentadienyl or tetramethylcyclopentadienyl; M1 is tetravalent titanium, zirconium or hafnium; X1 is chloro, fluoro, bromo, methyl, ethyl, propyl, butyl, pentyl, methoxy, ethoxy, propoxy, butoxy or dimethylamino.

On the other hand, the transition metal compound represented by the general formula (1) can be used as an active catalyst component used in polypropylene polymerization by extracting a ligand in the transition metal compound and cationizing the center metal, thereby forming a counter ion having weak bonding force, A compound or a boron compound, or a mixture thereof as a cocatalyst.

The boron compound which can be used as a cocatalyst in the present invention is a boron compound which is known in U.S. Patent No. 5,198,401, and can be specifically selected from the compounds represented by the following formulas (2) to (4).

(2)

B (R ¹¹ ) ₃

(3)

[R ₁₂ ] ⁺ [B (R ¹¹ ) ₄ ] ^-

[Chemical Formula 4]

_{^{[(R 13) r ZH]}} + [B (R 11) 4] -

In formulas (2) to (4), B is a boron atom; (C1-C20) alkyl substituted by a fluorine atom, (C1-C20) alkoxy substituted by a fluorine atom, and (C1-C20) ≪ / RTI > R ¹² is a (C5-C7) aromatic radical or a (C1-C20) alkyl (C6-C20) aryl radical or a (C6-C20) arylC1-C20) alkyl radical; Z is a nitrogen or phosphorus atom; R ¹³ is an (Cl-C20) alkyl radical or an Anilinium radical substituted with two (C1-C10) alkyls together with the nitrogen atom; r is an integer of 2 or 3;

Preferable examples of the boron-based co-catalyst include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluoro Phenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) (2,3,5,6-tetrafluorophenyl) borate, triphenylmethylniumtetrakis (2,3,4,6-tetrafluorophenyl) borate, triphenylmethyleniumtetrakis (pentafluorophenyl) (3,4,5-trifluorophenyl) borate, triphenylmethyllinium tetrakis (2,2,4-trifluorophenyl) borate, triphenylmethyllithium tetrakis , Triphenylmethyllinium phenylbis (pentafluorophenyl) borate or triphenylmethyllinium tetrakis (3,5-bistrifluoromethylphenyl) borate The can. Specific examples of these compounds include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, triphenyl (Pentafluorophenyl) borate, triphenylmethylium tetrakis (pentafluorophenyl) borate, triphenylmethyllithium tetrakis (3,5-bistrifluoromethylphenyl) borate, triethylammonium tetrakis (pentafluoro Tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl anilinium tetrakis (pentafluorophenyl) , 6-phen (Pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) Borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, or tri (dimethylphenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis Phenyl) phosphonium tetrakis (pentafluorophenyl) borate, of which the most preferred are N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylmethylniumtetrakis (pentafluorophenyl) ) Borate or tris (pentafluoro) borane.

Examples of the aluminum compound which can be used as a cocatalyst include an aluminoxane compound represented by Chemical Formula 5 or 6, an organoaluminum compound represented by Chemical Formula 7, or an organoaluminum alkyloxide or organoaluminum aryloxide compound represented by Chemical Formula 8 or Chemical Formula 9 have.

[Chemical Formula 5]

- [Al (R14) -O] _s-

[Chemical Formula 6]

(R ¹⁴ ) ₂ Al- [O (R ¹⁴ )] _t - (R ¹⁴ ) ₂

(7)

(R15) uAl (E) 3-u

[Chemical Formula 8]

(R ¹⁶ ) ² AlOR ¹⁷

[Chemical Formula 9]

R ^{16 is} Al (OR ¹⁷ ) ₂

In formulas (5) to (9), R14 is (C1-C20) alkyl; s and t are each independently an integer of 5 to 20; R ¹⁵ and R ¹⁶ are each independently (C 1 -C 20) alkyl; E is a hydrogen atom, a halogen atom or (C1-C20) alkyl; u is an integer from 1 to 3; R < ¹⁷ > is (C1-C20) alkyl or (C6-C20) aryl.

Specific examples of the aluminum compound include aluminoxane compounds such as methyl aluminoxane, modified methyl aluminoxane, and tetraisobutyl aluminoxane; Examples of the organoaluminum compound include trialkylaluminum including trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum and trioctylaluminum; Dialkyl aluminum chlorides, including dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride, and dihexyl aluminum chloride; Alkylaluminum dichlorides including methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, and hexylaluminum dichloride; Dialkylaluminum hydrides including dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride and dihexyl aluminum hydride, preferably aluminoxane compounds, tri Alkyl aluminum or mixtures thereof, more preferably methyl aluminoxane, modified methyl aluminoxane, triethyl aluminum, triisobutyl aluminum, or mixtures thereof.

In the transition metal catalyst composition according to the present invention, when the aluminum compound, particularly the aluminoxane compound, is used as a cocatalyst, the ratio of the transition metal (M): aluminum atom (Al) in the formula (1) is 1:10 to 5,000 , And more preferably from 1: 100 to 2,000. In the transition metal catalyst composition according to the present invention, the preferable range of the ratio between the transition metal compound represented by the formula (1) and the cocatalyst is a ratio of the central metal (M): boron atom (B): aluminum atom (Al) 0.1 to 200: 10 to 1,000, more preferably 1: 1 to 20: 10 to 500. It is possible to produce the polypropylene resin at the above ratio, and the range of the ratio varies depending on the purity of the reaction.

Since the catalyst composition presented in the present invention is present in a uniform form in a polymerization reactor, it is preferable to apply to a solution polymerization process carried out at a temperature above the melting point of the polymer. However, it may also be used for slurry polymerization or gas phase polymerization in the form of a non-uniform catalyst composition obtained by supporting the transition metal catalyst and cocatalyst on a porous metal oxide support as disclosed in U.S. Patent No. 4,752,597. Therefore, when the catalyst composition of the present invention is used together with an inorganic carrier or an organic polymer carrier, it can be applied to a slurry or a gas phase process. That is, the transition metal compound and the promoter compound may be supported on an inorganic carrier or an organic polymer carrier.

The method for producing a polypropylene resin according to the present invention is produced by polymerizing propylene and a diene compound of C4-C20 in the presence of the above transition metal catalyst composition. At this time, the transition metal catalyst and the cocatalyst component may be separately introduced into the reactor, or the respective components may be premixed and introduced into the reactor, and there are no particular restrictions on the mixing conditions such as the order of introduction, temperature or concentration.

The diene compound may be at least one selected from the group consisting of aliphatic dienes and aromatic dienes having 4 to 20 carbon atoms such as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8 - nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadien, 1,12-tridecadiene and 1,13-tetradecadiene; It may be a mixture of two or more.

At this time, the diene compound may be contained in an amount of 0.001 to 4 mol%, preferably 0.005 to 2 mol%, more preferably 0.01 to 1 mol%. If the content is out of the above range, the catalytic activity may be lowered or the thermal characteristics may be undesirably improved in terms of improving the melt tension.

The polypropylene resin produced according to the present invention has a branching index of 0.95 or less, a graft density of 0.005 or more, a gel content of 5 wt% or less and a melt tension (ARES (Advanced Rheometric Expansion System) Melt Strength ) Is more than 5g. In this case, the gel content may preferably be 2% by weight or less, and in the case of the melt tension, 10 g or more, and more preferably 30 g or more.

The polypropylene resin produced according to the present invention may have a weight average molecular weight of 30,000 to 3,000,000, preferably 70,000 to 2,000,000, and more preferably 100,000 to 1,000,000. The molecular weight distribution (MWD) may be 3 or more, preferably 3 to 15, and more preferably 3 to 10. The flow flow index (MFR) may be 0.1 to 100 g / 10 min, preferably 0.1 to 50 g / 10 min, and more preferably 0.5 to 25 g / 10 min. The melting point may be 160 占 폚 or lower, preferably 155 占 폚 or lower, and the upper limit of the melting point depends on the specific use, but is not typically higher than 165 占 폚. And the melting peak is preferably 160 占 폚 or lower.

The product such as a plastic molded article produced using the polypropylene resin produced according to the present invention is not limited in its field of use but can be preferably used mainly for automobile interior and exterior materials and specifically includes automobile interior foamed film / Parts, thermoformed products, trays, sound insulating materials, insulating materials, large hollows, and automotive parts.

Hereinafter, a specific embodiment of the present invention will be described.

Except where otherwise noted, all ligand and catalyst synthesis experiments were carried out using standard Schlenk or glovebox techniques under a nitrogen atmosphere, and the organic solvents used for all reactions were refluxed under sodium metal and benzophenone to yield water And the product was distilled immediately before use. 1 ^H -NMR analysis of the synthesized ligand and catalyst was performed using Bruker 300 MHz at room temperature.

The polymerization solvent, n-hexane, was passed through a tube filled with 5A molecular sieve and activated alumina and bubbled with high purity nitrogen to sufficiently remove water, oxygen and other catalyst poison substances. All the polymerization was carried out by introducing the required amount of solvent, co-catalyst, monomers to be polymerized, etc. in a high-pressure reactor (autoclave) completely blocked with the external air and then adding the catalyst. The polymerized polymer was analyzed according to the following method.

(1) Weight average molecular weight (Mw) and molecular weight distribution (MWD)

PL Mixed-BX2 + preCol-loaded PL210 GPC at 135 ° C at a rate of 1.0 mL / min in 1,2,3-trichlorobenzene solvent, and the molecular weight was corrected using a PL polystyrene standard material.

(2) Melting point (Tm) analysis

Using Dupont DSC2910 was measured at 2 ^nd heating condition at a rate of 10 ℃ / min in a nitrogen atmosphere.

(3) Branching index

The viscosity / linear PP viscosity of the branched PP was measured according to the following formula (1).

(4) Graft density < RTI ID = 0.0 >

13C NMR.

(5) Gel content

The gel content was measured according to the method of ASTM D2765. The dried product was pulverized, placed in xylene, and extracted at boiling point for 12 hours to determine the residual amount. At this time, the percentage of the remaining sample after extraction with respect to the weight of the sample before extraction was regarded as the gel content.

(6) Flow Flow Index (MFR)

After heating each cylinder at a temperature of 0 to 230 ° C in accordance with ASTM D 1238, a piston of 2.16 kg was placed in the cylinder and the weight of the resin passed through the orifice (inner diameter: 2.09 mm, length: 8 mm) And converted into the amount of passage for 10 minutes.

(7) Melt Strength (ARES (Advanced Rheometric Expansion System) Melt Strength)

A specimen with a width of 20 mm, a length of 10 mm and a thickness of 7 mm produced by hot press melting or injection was fixed to a sample holder at 190 ° C. using a Rheometric measuring instrument (2KFRTN, TA Instrument), and the sample holder The melt tension was measured by the resistance value of the specimen.

(8) link-link linear polymer average molecular weight

(Polymer 44 (2003) 7181-7188). ≪ tb > < TABLE >

Transition metal compound ( Tetramethylcyclopentadienyl Dimethylsilyl  2- methyl -4- (4-t- part Butylphenyl) Indeny  zirconium Dichloride ( Tetramethylcyclopentadienyl dimethylsilyl  2-methyl-4- (4-tert-butylphenyl) indenyl Zr  dichloride

1) Synthesis of dimethyl tetramethylcyclopentadienyl chlorosilane (dimethyl tetramethylcyclopentadienyl chlorosilane)

N-BuLi (2.5 M hexane solution) (170 ml) was slowly added dropwise at -10 ° C under a nitrogen atmosphere, followed by dropwise addition of 12 (trimethylsilyl) methylene chloride Lt; / RTI > for 1 hour. The temperature of the reaction solution was lowered to -10 ° C again, and then dimethyldichlorosilane (170 g) was added thereto. The mixture was stirred at room temperature for 12 hours for reaction, and then the reaction product was vacuum-dried. Hexane (500 ml) was added thereto to dissolve the reaction product. The reaction product was filtered through a Celite filter, and the filtered solution was vacuum-dried to obtain 70 g of dimethyl tetramethylcyclopentadienyl chlorosilane in the form of yellow oil (yield: 80%).

^{1 H-NMR (300 MHz,} CDCl3) δ 0.235 (s, 6H), 1.81 (s, 6H), 1.97 (s, 6H), 3.07 (s, 1H)

2) Synthesis of dimethyl tetramethylcyclopentadienyl 2-methyl-4- (4-t-butylphenyl) indenyl silane (Dimethyl tetramethylcyclopentadienyl 2-methyl-4- (4-tert-butylphenyl) indenyl silane)

The flask charged with toluene (200 ml), tetrahydrofuran (40 ml) and 2-methyl-4- (4-t-butylphenyl) indene (50 g) was cooled to -10 ° C and n-BuLi M hexane solution) (76 ml) was slowly added dropwise thereto, followed by stirring at room temperature for 12 hours. The temperature of the reaction mixture was lowered to -10 DEG C again, and then dimethyltetramethylcyclopentadienylchlorosilane (38 g) was added thereto, followed by stirring at room temperature for 12 hours. After completion of the reaction, water (400 ml) was added thereto, and the mixture was stirred at room temperature for 1.5 hours. Then, the mixture was extracted with toluene and vacuum dried to obtain dimethyltetramethylcyclopentadienyl 2- -Butylphenyl) indenylsilane (yield: 95%).

^{1 H-NMR (300 MHz,} CDCl3) δ 0.2-0.23 (d, 6H), 1.44 (s, 9H), 1.91 (s, 6H), 2.05-2.08 (d, 6H), 2.29 (s, 3H), 2.41 (s, 1 H), 3.76 (s, 1 H), 6.87 (s, 1 H)

3) Tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenyl

Synthesis of zirconium dichloride (Tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4- (4-tert-butylphenyl) indenyl Zr dichloride)

Dimethyl tetramethylcyclopentadienyl 2-methyl-4- (4-t-butylphenyl) indenylsilane (50 g), toluene (300 ml) and diethyl ether (100 ml) , And n-BuLi (2.5 M hexane solution) (90 ml) was slowly added dropwise. After dropwise addition, the reaction temperature was raised to room temperature, stirred for 48 hours, and then filtered. The obtained filtrate was vacuum-dried to obtain 40 g (yield 80%) of tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenyldilithium salt as a solid, And used immediately in the next reaction.

Tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenyldilithium salt (40 g), toluene (40 ml) and ether (10 ml) were placed in a flask . In Flask # 2, a mixture of toluene (30 ml) and ZrCl ₄ (20 g) was prepared. The mixture of flask # 2 was slowly dropped into flask # 1 with a cannula, and then stirred at room temperature for 24 hours. After stirring, the mixture was vacuum-dried, extracted with methylene chloride (500 ml), filtered through a Celite filter, and then the filtrate was vacuum-dried. The resulting solid was washed with a 1: 3 mixture of methylene chloride and n-hexane (50 ml) and vacuum dried to obtain tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t -Butylphenyl) indenyl zirconium dichloride (yield: 60%).

¹ H-NMR (300 MHz, CDCl 3)? 1.09 (s, 3H), 1.202 (s, 3H), 1.346 (s, 9H), 1.887-1.911 s, 3H), 2.278 (s, 3H), 7.0-7.628 (m, 8H)

Example  One

The inside of a stainless steel autoclave having an internal capacity of 2 L at room temperature was completely replaced with nitrogen. Triisobutylaluminum (2 ml of a 1 M solution in hexane), and 500 g of propylene and 0.25 ml of 1,7-octadiene were poured into the reactor while keeping the nitrogen purging, and then 50 mg of the catalyst compound and 1 ml of mineral oil And added to the reactor. Thereafter, polymerization was carried out at 70 DEG C for 60 minutes. After completion of the polymerization, the reactor was cooled to room temperature and the excess propylene was removed through a discharge line to obtain a white powdery solid. The resulting white solid powder was dried for 15 hours or more while heating to 80 캜 using a vacuum oven to prepare a final polypropylene resin.

Example  2

A polypropylene resin was prepared in the same manner as in Example 1 except that 0.5 ml of 1,7-octadiene was used in Example 1.

Example  3

A polypropylene resin was prepared in the same manner as in Example 1 except that 1 ml of 1,7-octadiene was used in Example 1.

Example  4

A polypropylene resin was prepared in the same manner as in Example 1 except that 5 mL of 1,7-octadiene was used in Example 1.

Example  5

A polypropylene resin was prepared in the same manner as in Example 3, except that 10 mg of hydrogen was used together with 1 ml of 1,7-octadiene in Example 3.

Example  6

A polypropylene resin was prepared in the same manner as in Example 4, except that 10 mg of hydrogen was used together with 5 ml of 1,7-octadiene in Example 4.

Comparative Example  One

A polypropylene resin was prepared in the same manner as in Example 1 except that 1,7-octadiene was not used in Example 1.

Comparative Example  2

A polypropylene resin was prepared in the same manner as in Example 1, except that 50 mL of 1,7-octadiene was used in Example 1.

The results of measurement of the physical properties of the polypropylene resin prepared according to the Examples and Comparative Examples are shown in Tables 1 and 2 below. Molecular weight distribution curves obtained by gel chromatography of the polypropylene resin prepared according to Example 1 are shown in Fig. 1 Respectively.

Referring to Table 1 and Table 2, it was found that when a diene-modified polypropylene resin was prepared by directly contacting propylene and an optimal amount of a diene compound using a specific metallocene catalyst system according to the present invention, And has a proper weight average molecular weight and a molecular weight distribution, it exhibits physical properties different from those of conventional copolymers, and thus has improved processability and physical properties suitable for improving melt tension. Also, it can be confirmed that the branching index and the graft density are improved, and the melt tension can be improved to the optimum level while maintaining the gel content at 5% or less.

The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning, range, and equivalence of the claims are included in the scope of the present invention Should be interpreted.

Claims (8)

The propylene and the diene compound are directly contacted with the metallocene catalyst so that the branching index is 0.95 or less, the graft density is 0.005 or more, the gel content is 5 wt% or less, and the melt tension (ARES Expansion System) Melt Strength) of 5 g or more. The method according to claim 1,
Wherein the diene compound is at least one selected from the group consisting of aliphatic dienes and aromatic dienes having 4 to 20 carbon atoms. 3. The method of claim 2,
The diene compound may be at least one selected from the group consisting of 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, - dodecadiene, 1,12-tridecadiene, and 1,13-tetradecadiene. The method according to claim 1,
Wherein the polypropylene resin contains the diene compound in an amount of 0.001 to 4 mol%. The method according to claim 1,
Wherein the polypropylene resin is a non-monomodal polypropylene resin having a molecular weight distribution of at least 3.0. The method according to claim 1,
Wherein the polypropylene resin has a flow flow index (MFR) of 0.1 to 100 g / 10 min. The method according to claim 1,
Wherein the polypropylene resin has a melting peak of 160 DEG C or less. The method according to claim 1,
Wherein the metallocene catalyst comprises a transition metal compound represented by the following formula (1).
[Chemical Formula 1]

M is 2 and n is 0 and M is 0 and n is 1 when M is a divalent transition metal of Group 4 in the periodic table; is M and η ⁵ - is a cyclopentadienyl ring which can be combined, wherein the cyclopentadienyl ring (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl, tri (C1- (C6-C20) arylsilyl, (C6-C20) arylsilyl, (C1-C20) alkyldi It can be further substituted with one or more selected from the group consisting of alkenyl and; D is SiR ³ R ⁴ or (C2-C20) alkenylene; R ³ and R ⁴ are each independently hydrogen, (C1-C20) alkyl, (C3-C20) or cycloalkyl, or (C6-C20) aryl, wherein R ³ and R ⁴ are (C4-C7) are connected by an alkylene to form a ring, and; R ¹ is (C1-C20) alkyl ; Ar is (C6-C20) aryl; R ² is hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl or (C6- C20) aryl; wherein Ar and R ² are (C1-C7) alkylene, (C2-C7) alkenylene or a (C4-C7) are connected to the alkane diethoxy alkenylene may form a fused ring; X ¹ is a halogen , (C1-C20) alkyl, (C1-C20) alkoxy, (C3-C20) cycloalkyl, (C6-C20) aryl, (C6-C20) ^{aryloxy, -OSiR a R b R c,} -SR d, -NR ^e R ^f or R ^h and -PR ^g; R ^a to R ^h are each independently (C1-C20) alkyl, (C6-C20) aryl or (C3-C20) cycloalkyl; X ² is a neutral conjugated or non-conjugated (C4-C20) diene, and; wherein the R ¹ alkyl, an Ar aryl, R ^2, R ³ and R ⁴ for alkyl, cycloalkyl, aryl are independently from each other are selected from halogen, (C1-C20) alkyl, Which may be further substituted with one or more substituents selected from the group consisting of halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy and have.)

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