KR20170037266A - Polyolefin copolymer and moleded body composition comprising the same - Google Patents
Polyolefin copolymer and moleded body composition comprising the same Download PDFInfo
- Publication number
- KR20170037266A KR20170037266A KR1020150136633A KR20150136633A KR20170037266A KR 20170037266 A KR20170037266 A KR 20170037266A KR 1020150136633 A KR1020150136633 A KR 1020150136633A KR 20150136633 A KR20150136633 A KR 20150136633A KR 20170037266 A KR20170037266 A KR 20170037266A
- Authority
- KR
- South Korea
- Prior art keywords
- compound
- polyolefin
- olefin
- mol
- borate
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a process for producing an aromatic vinyl compound, which comprises an olefin compound, an alpha-olefin compound, a diene compound and an aromatic vinyl compound, wherein the olefin compound is 10 to 90 mol%, the alpha-olefin compound is 0.1 to 50 mol%, the diene compound is 0.1 to 10 mol% 0.1 to 50 mol% of the polyolefin-based copolymer.
Description
The present invention relates to a polyolefin-based copolymer and a molded article comprising the same.
Recently, in the automobile industry, the weight of the vehicle body has been reduced in order to improve the fuel efficiency of automobiles. As a result, the amount of plastic used in automobile parts is increasing. Particularly, polypropylene (PP) in synthetic resin is relatively low in cost and has high processability, so it occupies about 1/3 of synthetic resin materials used for parts for all automobile interior and exterior materials, and its usage is increasing. However, automobile interior and exterior materials made of a resin composition containing only polypropylene have insufficient strength and shock absorbing ability, and have a problem of having a hard texture unique to a synthetic resin. In order to solve such a problem, it is possible to produce automotive interior and exterior materials having improved physical properties such as high fluidity, high strength, high impact resistance and low gloss by using a polyolefin-based copolymer produced by polymerizing polypropylene and other compounds . However, the resin composition containing polypropylene can improve the fluidity of the automotive interior and exterior materials, but still has a problem that the mechanical strength (flexural modulus) and impact resistance are lowered.
Accordingly, when rubber is added to the resin composition in order to compensate for the impact resistance, the mechanical strength of the automobile interior and exterior materials can be reduced. When the inorganic filler is added to the resin composition to compensate the mechanical strength, Can be increased. In addition, automobile interior materials such as glove box, console, and center crash pad should satisfy not only the impact resistance but also the aesthetic effect of the driver. Therefore, the scratch resistance and the low glossiness must be improved at the same time.
Accordingly, a silicone compound, a fluorine compound, or the like may be added to the polyolefin resin composition in order to improve the scratch resistance. However, when a silicone compound is added to the polyolefin-based resin composition, migration of silicon to the surface of the resin composition occurs easily at the time of molding, so that gas is generated on the surface of the resin composition or the surface is uneven due to excessive gloss There is a problem that the physical properties of the product are also reduced. Further, when a fluorine-based compound is added to the polyolefin-based resin composition, the cost of the fluorine-based compound is high and the production cost may increase, and the physical properties of the resin composition may easily change according to the molding conditions. There is a problem that the luxurious feel of the product is deteriorated.
In order to produce automotive interior and exterior materials having desired physical properties, it is necessary to control the kinds of the compounds used in the resin composition and the amounts thereof to be used, and studies on such compounds are still necessary.
In order to solve the above problems, it is an object of the present invention to provide a polyolefin-based copolymer capable of improving scratch resistance while maintaining the mechanical strength (elastic modulus) of a polyolefin-based resin composition used as an automotive interior and exterior material.
The present invention also provides a molded article comprising the polyolefin-based copolymer.
In order to attain the above object, the present invention provides an olefin resin composition comprising 10 to 90 mol% of an olefin compound, 0.1 to 50 mol% of an alpha olefin compound, 0.1 to 10 mol% of a diene compound, mol% and an aromatic vinyl compound in an amount of 0.1 to 50 mol%.
The present invention also provides a molded article comprising the polyolefin-based copolymer.
The polyolefin-based copolymer of the present invention can provide a polyolefin-based resin composition improved in scratch resistance while maintaining mechanical strength (elastic modulus).
Therefore, the polyolefin-based resin composition can be applied to automotive interior and exterior materials having improved scratch resistance.
Polyolefin resin compositions including polyethylene (PE) and polypropylene (PP) are excellent in physical properties, and can be used as interior and exterior materials for automobiles due to their low specific gravity and low cost. Such a polyolefin resin composition includes a linear alpha olefin compound as an additive such as a cleaning agent, a lubricant, a plasticizer and the like, and may further include a scratch-improving agent. However, the resin composition containing the scratch-improving agent has a disadvantage that gloss is increased.
Accordingly, the present invention provides a polyolefin-based copolymer for improving the scratch resistance while maintaining the mechanical strength (modulus of elasticity) of the polyolefin-based resin composition used in manufacturing automotive interior and exterior materials.
The polyolefin-based copolymer of the present invention is composed of a certain amount of an olefin compound, an alpha-olefin compound, a diene compound, and an aromatic vinyl compound. At this time, the olefin compound, the alpha-olefin compound and the diene compound are first polymerized into the olefin-alpha olefin-diene copolymer by the high catalytic activity of the specific main catalyst compound and the cocatalyst compound. The olefin-alpha olefin-diene copolymer is subjected to secondary polymerization with an aromatic vinyl compound in the presence of an anionic catalyst compound to improve scratch resistance while maintaining elasticity to form a polyolefin-based copolymer. Such a polyolefin-based copolymer is a graft copolymer in which an aromatic vinyl compound is effectively introduced into a diene compound having a carbon-carbon double bond in an olefin-alpha olefin-diene copolymer in a graft form, and can exhibit desired properties.
On the other hand, when a diene compound is added to the olefin compound and the alpha-olefin compound, a post-treatment step is required, so that the preparation time and cost are additionally required. However, when the amount of the olefin compound, the alpha olefin compound, It is possible to obtain a copolymer at a high yield.
≪ Polyolefin-based copolymer &
The polyolefin-based copolymer of the present invention contains an olefin compound, an alpha-olefin compound, a diene compound and an aromatic vinyl compound in a specified amount and can be provided as a polyolefin-based resin composition.
Wherein the polyolefin copolymer is composed of an olefin compound, an alpha-olefin compound, a diene compound and an aromatic vinyl compound, wherein the olefin compound is 10 to 90 mol%, the alpha-olefin compound is 0.1 to 50 mol%, the diene compound is 0.1 to 10 mol% The vinyl compound is contained in an amount of 0.1 to 50 mol%, which will be described in detail as follows.
The olefin compound used in the present invention is not particularly limited and may be at least one selected from the group consisting of ethylene, propylene and butene. At this time, the olefin compound is preferably ethylene.
The alpha-olefin compound used in the present invention is not particularly limited and may be at least one selected from the group consisting of propylene, butene, pentene, hexene, propene and octene. At this time, it is preferable that the alpha-olefin compound is propylene.
The diene compound used in the present invention is not particularly limited and may be at least one selected from the group consisting of vinyl aromatic compounds, butadiene, isoprene, alkyl acetates, alkyl methacrylates, vinyl amides and vinyl pyridines. At this time, the diene compound is preferably a vinyl aromatic compound, and it is preferably divinylbenzene.
The aromatic vinyl compound used in the present invention may be any conventional aromatic vinyl compound known in the art. At this time, the aromatic vinyl compound is preferably styrene.
The olefin compound, the alpha-olefin compound and the diene compound may be prepared by reacting a main catalyst compound comprising a compound represented by the following formula (1) with at least one promoter compound selected from the group consisting of compounds represented by the following formulas / RTI > olefin-alpha olefin-diene copolymer in the presence of a < RTI ID = 0.0 >
The main catalyst compound is a compound containing a transition metal represented by the following general formula (1), and the olefin-alpha olefin-diene copolymer can be polymerized by high catalytic activity.
[Chemical Formula 1]
In Formula 1,
M is selected from the group consisting of Group 4 elements on the periodic table and is preferably selected from the group consisting of titanium (Ti), zirconium (Zr), and hafnium (Hf).
Q 1 and Q 2 are the same or different and each independently halogen, (C 1 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 2 -C 20) alkynyl each other, (C 6 - C 20) aryl, alkyl amido (C 1 -C 20) alkyl (C 6 -C 20) aryl, (C 6 -C 20) aryl (C 1 -C 20) alkyl, (C 1 -C 20) degrees, (C 6 -C 20 ) arylamido and (C 1 -C 20 ) alkylidene, and is preferably methyl or chlorine.
R 1 to R 10 are the same 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; And (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 form a ring are connected to each other, R 5 and R 6, R 6 and R 7, R 7 and R 8, R 8 and R 9 or R 9 And 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.
At this time, R 11 and R 12 or R 12 and R 13 may be connected to each other to form a ring.
Preferably, R 1 to R 5 are hydrogen or methyl, and R 6 to R 13 are all hydrogen.
Wherein the main catalyst compound comprises a ligand of a novel structure in which an amido ligand and ortho-phenylene form a condensed ring and the pentagonal ring pi-ligand bound to the ortho-phenylene is fused by a thiophene heterocycle do. Therefore, when the olefin compound, the alpha olefin compound and the diene compound are polymerized, the main catalyst compound can exhibit a higher catalytic activity than the transition metal compound not having the thiophene heterocycle fused thereto.
The main catalyst compound represented by the general formula (1) is effective for controlling the electronic and stereoscopic environment around the metal including the substituent.
Further, the above-mentioned promoter compound is a promoter compound of any one of the compounds represented by the following general formulas (2) and (3). At this time, the promoter compound serves to activate the main catalyst compound represented by the above formula (1).
(2)
[LH] + [Z (A) 4 ] -
(3)
[L] + [Z (A) 4 ] -
In the above Formulas 2 and 3,
L is a neutral or cationic Lewis acid.
Z is selected from the group consisting of Group 13 elements on the periodic table.
A are the same or different, each independently represent at least one hydrogen atom is halogen, (C 1 -C 20) hydrocarbyl, (C 1 -C 20) alkoxy (C 6 -C 20) aryl, (C substituted with 1 -C 20) alkoxy substituted with (C 1 -C 20) alkyl radical, (C 6 -C 20) aryloxy radicals substituted with a (C 6 -C 20) aryl and (C 6 -C 20) aryloxy (C 1 -C 20 ) alkyl radical substituted with a radical.
The promoter compound represented by the above formula (2) or (3) has strong electrophilicity and rapidly dissociates Q 1 and / or Q 2 bound to the center metal M of the main catalyst compound represented by the above formula (1). At this time, as the dissociation of Q 1 and / or Q 2 becomes faster, the polymerization activity increases, and as the time for stabilization of the center metal M becomes longer, the stabilized M becomes more stable as the olefin compound, the carbon- As long as the double bond and the coordination are long, a high molecular weight olefin-alpha olefin-diene copolymer can be obtained.
Considering the activity of the main catalyst compound, in the co-catalyst compound represented by the above formula (2), the [LH] + is dimethylanilinium cation dimethyl, wherein [Z (A) 4] - is [B (C 6 F 5 ) 4 ] - .
Here, the promoter compound represented by Formula 2 is not particularly limited and examples thereof include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (penta (Pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) (Sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) (N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate), N, N-dimethylanilinium n-butyltris (pentafluoro N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) N, N-dimethylanilinium tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) 3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (t-triisopropylsilyl) -2,3,5,6-tetrafluorophenyl) dimethylanilinium tetrakis (4- (triisopropysylyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium pentafluorophenoxytris (pentafluorophenyl) borate (N, N-dimethylanilinium pentafluorophenoxytris pentafluorophenyl borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylaniline Tetrakis (pentafluorophenyl) borate, N, N-dimethylammonium tetrakis (2,3,5,6-tetrafluoro Phenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) 3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophcnyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis ) Ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) Kiss (2,3,4,6-tetrafluorophenyl) borate (N, N-dim N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) , 3,4,6-tetrafluorophenyl) borate, N, N-dimethyl 2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) 2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate (di- pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, and the like.
[L] + is [(C 6 H 5 ) 3 C] + , and [Z (A) 4 ] is the same as that of the main catalyst compound, ] - is preferably [B (C 6 F 5 ) 4 ] - .
Herein, the promoter compound represented by Formula 3 is not particularly limited, and examples thereof include triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (o-tolyl) (Pentafluorophenyl) borate, tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate (tri (2,6-dimethylphenyl) trialkylphosphonium salts such as diphenyloxonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) oxonium tetrakis (pentafluorophenyl) borate, Di (o-tolyl) oxonium tetrakis (pentafluororphenyl) borate, di (2,6-dimethylphenyloxonium tetrakis (pentafluorophenyl) borate di (2,6-dimethylphenyl oxonium tetrakis (pe (pentafluorophenyl) borate, diphenylsulfonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) borate (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate ), Triphenylmethylcarbenium tetrakis (pentafluorophenyl) borate, triphenylmethylcarbenium tetrakis (pentafluorophenyl) borate, triphenylmethylcarbenium tetrakis (pentafluorophenyl) , Benzene (diazonium) tetrakis (pentafluorophenyl) borate), and the like; It may be a trialkylaluminum such as trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum.
The amount of the main catalyst compound and the co-catalyst compound to be used is not particularly limited, and it is preferable that the main catalyst compound and the co-catalyst compound are mixed in the following proportions in consideration of catalytic activity and production cost.
The amount of the main catalyst compound (M) represented by the formula (1) and the promoter compound (Z) represented by the general formulas (2) and (3) is preferably from 1: 1 to 100,000 , Preferably from 1: 1 to 10,000, more preferably from 1: 1 to 5,000.
More specifically, the amount of the main catalyst compound (M) represented by Formula (1) and the amount of the co-catalyst compound (Z) represented by Formula (2) : 1 to 1: 100, preferably 1: 1 to 10, more preferably 1: 1 to 4.
The main catalyst compound represented by the formula (1) may be used alone or in combination with the main catalyst compound and the promoter compound represented by the general formulas (2) and (3) on a carrier to be used for polymerization of an olefin compound, an alpha olefin compound and a diene compound . At this time, as the carrier, an inorganic or organic carrier used in the production of catalysts known in the art can be used without limitation.
The polymerization of the olefin-alpha olefin-diene copolymer may be carried out in a slurry phase, a solution phase, a gas phase, or a bulk phase.
When the polymerization reaction is carried out in a liquid phase or a slurry, a solvent, an olefin compound or an alpha-olefin compound itself may be used as a medium.
The solvent which can be used in the polymerization reaction may be selected from the group consisting of 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.
At this time, the amount of the main catalyst compound may be determined within a range in which the polymerization reaction of the monomers can sufficiently take place in the slurry, liquid phase, gas phase or massive process, and is not particularly limited.
However, according to the present invention, the addition amount of the main catalyst is 10 -8 to 1 mol / L, preferably 10 (mol / L) based on the concentration of the central metal (M) of the main catalyst compound per unit volume -7 to 10 - 1 mol / L, more preferably from 10 -7 to 10 may be a 2 mol / L.
The polymerization reaction may be carried out in a batch type, semi-continuous type or continuous type reaction.
The polymerization temperature and pressure conditions are not particularly limited and can be determined in consideration of the efficiency of the polymerization reaction depending on the kind of the reaction to be applied and the type of the reactor.
However, according to the present invention, the polymerization temperature may be 100 to 200 ° C, preferably 120 to 160 ° C, and the polymerization pressure may be 1 to 3000 atm, preferably 1 to 1000 atm.
Also, the olefin-alpha olefin-diene copolymer may be subjected to secondary polymerization with the aromatic vinyl compound in the presence of an anionic catalyst compound represented by the following formula (4) to provide a final polyolefin-based copolymer.
[Chemical Formula 4]
[P-Li]
In Formula 4,
P is (C 1 -C 20 ) alkyl and is preferably selected from the group consisting of ethyl, methyl, propyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.
The anionic catalyst compound represented by the general formula (4) is obtained by polymerizing an olefin-alpha olefin-diene copolymer by introducing an aromatic vinyl compound into a vinyl group of a diene in a grafted form to obtain a polyolefin graft copolymer.
More specifically, the anionic catalyst compound may be prepared by first reacting an anion with vinyl of a diene in an olefin-alpha olefin-diene copolymer, and then introducing an aromatic vinyl compound into the olefin-alpha olefin-diene-aromatic graft copolymer The coalescence can be polymerized.
Alternatively, the anionic catalyst compound may be prepared by first reacting with the vinyl group of the aromatic vinyl compound to activate the anion, and then reacting the vinyl group of the diene with the anion and the vinyl group of the olefin-alphaolefin-diene copolymer to form an olefin- An aromatic graft copolymer can be polymerized.
At this time, the polymerization reaction using the anionic catalyst compound may be performed without limitation for anion polymerization conditions known in the art.
Meanwhile, the polyolefin-based copolymer of the present invention produced as described above may have a flow flow index (MFR) of 0.01 to 100 g / 10 min, preferably 0.1 to 50 g / 10 min.
The polyolefin-based copolymer of the present invention may have a density of 0.860 to 0.910 g / cm 3 and a surface hardness (Shore A) of 50 to 100.
At this time, the polyolefin-based copolymer having the flow flow index, density and surface hardness in the above range can be applied to a polyolefin-based resin composition which is a material for automotive interior and exterior materials.
The polyolefin-based copolymer may have a weight average molecular weight (Mw) of 1,000 to 2,000,000 g / mol, preferably 10,000 to 1,500,000 g / mol, more preferably 10,000 to 1,000,000 g / mol.
The polyolefin-based copolymer may be thermally stable for processing or molding the resin composition containing the polyolefin-based copolymer when the glass transition temperature is from -80 to 0 캜.
< Shaped body >
The present invention provides a molded article comprising the polyolefin-based copolymer.
The molded article can be produced as a product exhibiting excellent scratch resistance while maintaining elasticity through processing and molding of a resin composition containing a polyolefin-based copolymer. Such a molded article can be used in various industrial fields, and particularly applicable to automobile interior and exterior materials.
EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples. However, the following Examples are illustrative of the present invention, but the present invention is not limited by the following Examples.
[ Example 1] Polyolefin-based copolymer
<First Polymerization>
After replacing the inside of the high-pressure reactor (internal volume: 2.8 L, stainless steel) with nitrogen at room temperature, 1 L of n-hexane and 2.0 mmol of triisobutylaluminum were added. Then, 250.0 mL of 1-octene and 2.0 mL of divinylbenzene (DVB) were injected. Then, 135.0 g of ethylene gas was introduced, and the reactor temperature was preheated to 140 캜. Then, a solution of dimethylanilinium tetrakis (pentabluorophenyl) borate promoter compound (45.0 μmol) was mixed in a mixed solution of the main catalyst compound (7.5 μmol) and triisobutylaluminum (187.5 μmol) and injected into the reactor for 5 minutes Lt; / RTI >
≪ Second polymerization >
When the first polymerization was completed, the temperature was lowered to 50 DEG C and the residual ethylene gas was removed. Thereafter, 20.0 mL of styrene was added to the reactor, and the temperature was raised to 80 캜. Then, an n -butyllithium ( n- BuLi) anion catalyst compound (0.5 mmol) was injected and polymerization was carried out for 30 minutes. After the completion of the second polymerization, the temperature was lowered to room temperature, excess ethylene was discharged, and the copolymer dispersed in the solvent was dried at 80 캜 in a vacuum oven to prepare a polyolefin-based copolymer.
[ Example 2] polyolefin-based copolymer
A polyolefin-based copolymer was prepared in the same manner as in Example 1, except that 40.0 mL of styrene was fed in < Second Polymerization >.
[ Example 3] Polyolefin-based copolymer
A polyolefin-based copolymer was prepared in the same manner as in Example 1, except that 5.0 mL of divinylbenzene was fed in < First Polymerization >.
[ Example 4] Polyolefin-based copolymer
A polyolefin-based copolymer was prepared in the same manner as in Example 1, except that 5.0 mL of divinylbenzene was fed in the first polymerization and 40.0 mL of styrene was fed in the second polymerization.
[ Example 5] Polyolefin-based copolymer
A polyolefin-based copolymer was prepared in the same manner as in Example 1, except that 10.0 mL of divinylbenzene was added in < First Polymerization >.
[ Example 6] polyolefin-based copolymer
A polyolefin-based copolymer was prepared in the same manner as in Example 1, except that 10.0 mL of divinylbenzene was fed in the first polymerization and 40.0 mL of styrene was fed in the second polymerization.
[ Comparative Example 1] Polyolefin-based copolymer
A polyolefin-based copolymer was prepared in the same manner as in Example 1, except that in the <first polymerization>, no divinylbenzene was injected and <second polymerization> was not carried out.
[ Comparative Example 2] polyolefin-based copolymer
A polyolefin-based copolymer was prepared in the same manner as in Example 1, except that 10.0 mL of divinylbenzene was fed in <First Polymerization> and <Second Polymerization> was not carried out.
[ Comparative Example 3] Polyolefin-based copolymer
A polyolefin-based copolymer was prepared in the same manner as in Example 1 except that 40.0 mL of styrene was injected in < Second polymerization > without injecting dibehenylbenzene in < First polymerization >.
The main catalyst compounds used in Examples 1 to 6 and Comparative Examples 1 to 3 have the following structures.
In addition, the amount of the main catalyst compound and the promoter compound used in Examples 1 to 6 and Comparative Examples 1 to 3 is a molar ratio of main catalyst compound: cocatalyst compound = 1: 6.
[ Experimental Example 1] Measurement of physical properties
The physical properties of the polyolefin-based copolymers prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Tables 1 and 2 below.
At this time, the weight average molecular weight (Mw) was measured by GPC (Gel Permeation Chromatography, PL-GPC220, manufacturer: Agilent).
The yield (dry weight) of the polyolefin-based copolymer was measured.
The polymerization activity was calculated by the following formula.
Polymerization activity (kg / mmol · hr) = (yield) / [(mmol of catalyst) * {(60) / (polymerization time)}]
The flow flow index (MFR, g / 10 min) was also measured according to ASTM D 1238 (230 캜, 2.16 Kg).
The density (g / cm 3 ) was also measured according to ASTM D 792.
The tensile strength (MPa) was measured according to ASTM D 638 (specimen thickness 3 mm, 23 캜).
The flexural modulus (MPa) was measured according to ASTM D 790 (specimen thickness 6 mm, 23 ° C).
In addition, the surface hardness was measured according to ASTM D 2240 by Shore A hardness.
The scratch resistance was evaluated using the scratch tester ERICHSEN 430P (Load 10 N) under the conditions and criteria described in Table 3 below.
In addition, the soft touch feeling was rated on the basis of the criteria shown in Table 4 below, with the degree of hardness and softness of the surface.
As shown in Tables 1 and 2, it was confirmed that the polyolefin-based copolymer produced in Examples 1 to 6 and Comparative Examples 1 to 3 exhibited MFR, density, and surface strength suitable for manufacturing automotive interior and exterior materials.
In addition, it was confirmed that the polyolefin-based copolymers prepared in Examples 1 to 6 were produced at a higher yield than the polyolefin-based copolymers prepared in Comparative Examples 1 to 3, and thus had high polymerization activity.
In addition, the polyolefin-based copolymers produced in Examples 1 to 6 had a broad molecular weight distribution as compared with the polyolefin-based copolymers prepared in Comparative Examples 1 to 3, and thus it was confirmed that the processability was improved and the scratch resistance was excellent. Especially, it was confirmed that the scratch resistance of the polyolefin-based copolymer was controlled depending on the content of styrene.
Claims (11)
A polyolefin-based copolymer containing 10 to 90 mol% of the olefin compound, 0.1 to 50 mol% of an alpha-olefin compound, 0.1 to 10 mol% of a diene compound and 0.1 to 50 mol% of an aromatic vinyl compound.
Wherein the olefin compound is at least one compound selected from the group consisting of ethylene, propylene and butene.
Wherein the alpha-olefin compound is at least one compound selected from the group consisting of propylene, butene, pentene, hexene, propene and octene.
Wherein the diene compound is at least one compound selected from the group consisting of a vinyl aromatic compound, butadiene, isoprene, alkyl acetate, alkyl methacrylate, vinyl amide and vinyl pyridine.
Wherein the olefin compound is ethylene,
Wherein the alpha olefin compound is octene,
Wherein the diene compound is divinylbenzene,
Wherein the aromatic vinyl compound is styrene.
And a flow flow index (MFR) of 0.1 to 100 g / 10 min.
And a surface hardness (Shore A) of 50 to 100. The polyolefin-
A density of 0.860 to 0.910 g / cm < 3 >
And a weight average molecular weight (Mw) of 10,000 to 1,000,000 g / mol.
And a glass transition temperature of -80 to 0 占 폚.
A molded article which is an automobile interior and exterior material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150136633A KR101766968B1 (en) | 2015-09-25 | 2015-09-25 | Polyolefin copolymer and moleded body composition comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150136633A KR101766968B1 (en) | 2015-09-25 | 2015-09-25 | Polyolefin copolymer and moleded body composition comprising the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20170037266A true KR20170037266A (en) | 2017-04-04 |
| KR101766968B1 KR101766968B1 (en) | 2017-08-09 |
Family
ID=58588408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150136633A KR101766968B1 (en) | 2015-09-25 | 2015-09-25 | Polyolefin copolymer and moleded body composition comprising the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101766968B1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050093186A (en) | 2004-03-18 | 2005-09-23 | 현대모비스 주식회사 | Polypropylene resin composition |
| KR20120028537A (en) | 2010-09-15 | 2012-03-23 | (주)씨앤테크 | Polyolefin resin composition with improved scratch resistance for preventing surface damage |
-
2015
- 2015-09-25 KR KR1020150136633A patent/KR101766968B1/en active IP Right Review Request
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050093186A (en) | 2004-03-18 | 2005-09-23 | 현대모비스 주식회사 | Polypropylene resin composition |
| KR20120028537A (en) | 2010-09-15 | 2012-03-23 | (주)씨앤테크 | Polyolefin resin composition with improved scratch resistance for preventing surface damage |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101766968B1 (en) | 2017-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6991132B2 (en) | Ziegler-Natta-metallocene binary catalyst system with activator-carrier | |
| EP3372620B1 (en) | Catalyst composition for synthesizing olefin copolymer, and method for preparing olefin copolymer | |
| JP6187332B2 (en) | Polyethylene for pipes and joints and molded articles thereof | |
| KR102260362B1 (en) | Olefin copolymer | |
| KR20180058703A (en) | Non-uniform Ziegler-Natta catalyst with fluorinated silica-coated alumina | |
| KR102086056B1 (en) | Polypropylene-based resin composition | |
| KR101528603B1 (en) | Method for preparing polyolfin and polyolefin prepared therefrom | |
| KR20210067264A (en) | Ethylene alpha-olefin copolymer | |
| KR20210067338A (en) | Composite resin composition comprising polypropylene and ethylene alpha-olefin copolymer | |
| KR20180067944A (en) | Olefin copolymer | |
| KR20210121043A (en) | Curable composition comprising unsaturated polyolefin | |
| EP3476867A1 (en) | Polyolefinic film | |
| EP1448633B2 (en) | Two-step polymerization process | |
| WO2017069538A1 (en) | Transition metal compound, catalyst composition comprising same and method for preparing polyolefin using same | |
| EP3336113A1 (en) | Microstructure-controlled copolymers of ethylene and c3-c10 alpha-olefins | |
| KR101766968B1 (en) | Polyolefin copolymer and moleded body composition comprising the same | |
| KR20180054357A (en) | Method for preararing polypropylene | |
| KR101835993B1 (en) | Catalyst for olefin polymerization and method for preparing polyolefin using the same | |
| KR101878047B1 (en) | Method of Manufacturing Brush-copolymerized Polymer Compound | |
| KR102649850B1 (en) | Thermoplastic resin composition excellent in softness and transparency and method for preparing same | |
| KR101986231B1 (en) | Polymer composition having improved scratch resistance | |
| KR20190063572A (en) | A metallocene catalyst system for producing polyethylene and a method for producing polyethylene by using the same | |
| JP5891901B2 (en) | Polyethylene and method for producing the same | |
| KR101811137B1 (en) | Method of Manufacturing Brush-copolymerized Polymer Compound | |
| KR101878046B1 (en) | Method of Manufacturing Brush-copolymerized Polymer Compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E90F | Notification of reason for final refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| Z031 | Request for patent cancellation [new post grant opposition system introduced on 1 march 2017] |
Free format text: CASE NUMBER: 2017106000077 |
|
| Z072 | Maintenance of patent after cancellation proceedings: certified copy of decision transmitted [new post grant opposition system as of 20170301] | ||
| Z131 | Decision taken on request for patent cancellation [new post grant opposition system as of 20170301] | ||
| Z072 | Maintenance of patent after cancellation proceedings: certified copy of decision transmitted [new post grant opposition system as of 20170301] | ||
| Z131 | Decision taken on request for patent cancellation [new post grant opposition system as of 20170301] |