KR101828929B1 - Compound for preparing polyolefin for preparing fiber and supported catalyst comprising the same - Google Patents
Compound for preparing polyolefin for preparing fiber and supported catalyst comprising the same Download PDFInfo
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- KR101828929B1 KR101828929B1 KR1020160015298A KR20160015298A KR101828929B1 KR 101828929 B1 KR101828929 B1 KR 101828929B1 KR 1020160015298 A KR1020160015298 A KR 1020160015298A KR 20160015298 A KR20160015298 A KR 20160015298A KR 101828929 B1 KR101828929 B1 KR 101828929B1
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- 0 C=CCCC1c2cccc(C*c3ccccc3)c2CC1 Chemical compound C=CCCC1c2cccc(C*c3ccccc3)c2CC1 0.000 description 3
Classifications
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
-
- 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
- C08F10/00—Homopolymers and 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
Abstract
The present invention provides a compound represented by the following formula (1), which can be usefully used for producing a polyolefin resin for fibers, a supported catalyst comprising the same, and a process for producing a polymer of polyolefin in the presence of the supported catalyst:
[Chemical Formula 1]
Wherein R 1 to R 7 , M, X 1 and X 2 are as defined in the specification.
Description
The present invention relates to a compound having a novel structure which can be usefully used for producing a polyolefin resin for fibers, a supported catalyst comprising the same, and a process for producing a polymer of polyolefin in the presence of the supported catalyst.
High-density polyethylene is used for producing high-strength yarns such as ropes, fishing nets and the like. Such high-density polyethylene is required to have properties such as high elongation and high strength.
In the above-mentioned textile products, it is known that the narrower the molecular weight distribution of the high-density polyethylene is, the better the mechanical properties are. That is, when the molecular weight distribution of the high-density polyethylene is narrow, the stretching ratio becomes high, and high strength can be obtained by high stretching. However, if the molecular weight distribution of the high-density polyethylene is too narrow, there is a problem that the workability becomes very poor.
The polyolefin resin produced using the conventional Ziegler-Natta catalyst has excellent processability, but has a disadvantage in that the low-molecular part elutes during processing and deteriorates the inherent physical properties of the resin, and has a limitation in improving the strength by broadening the molecular weight distribution. In the case of the metallocene catalyst, the catalytic activity is high and the molecular weight distribution of the polyolefin resin produced by using the metallocene catalyst is low, thereby improving the disadvantages of the Ziegler-Natta catalyst. On the other hand, the disadvantage of producing a polyolefin having low abrasion strength and poor processability .
There is a disadvantage in that it is difficult to obtain a homogeneous polymer due to the different reactivity of each catalyst, although a hybrid supported catalyst in which two or more kinds of metallocene catalysts are also carried on a carrier has been developed. Particularly, since an ultra-high molecular weight polymer is produced and formed into a gel in a resin, it is a cause of single yarns in the process of spinning for fiber use.
Accordingly, in the present invention, a metallocene catalyst is used, and two anion structures coordinating a central metal atom are different from each other, and a catalyst suitable for the production of a polyolefin resin for fibers by controlling the substituent of each anion structure has been developed.
In order to solve the above problems, the present invention provides a compound represented by the following formula (1).
The present invention also provides a supported catalyst comprising a compound represented by the following general formula (1) and a carrier.
The present invention also provides a process for producing a polyolefin polymer in the presence of the supported catalyst.
In order to solve the above problems, the present invention provides a compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]
In this formula,
R 1 is NR a R b ,
Wherein R a and R b are each independently hydrogen, C 1-10 alkyl, C 3-10 cycloalkyl, or C 6-10 aryl,
R 2 is C 2-20 alkenyl,
R 3 to R 7 are each independently selected from the group consisting of hydrogen, C 1-20 alkyl, C 1-20 alkoxy, C 2-20 alkenyl, C 6-20 aryl, C 7-20 alkylaryl, C 7-20 arylalkyl, C 3-20 cycloalkyl, or C 5-20 heteroaryl,
M is a Group 4 transition metal,
X 1 and X 2 are each independently selected from the group consisting of halogen, C 1-20 alkyl, C 2-20 alkenyl, C 6-20 aryl, nitro, amido, C 1-20 alkylsilyl, C 1-20 alkoxy, C 1-20 sulfonate.
The present invention provides a catalyst for producing a polyolefin resin for fibers, wherein the polyolefin resin for fibers should have a uniform molecular weight distribution over a proper level in order to have high strength and high elongation characteristics inherent in the fibers. Accordingly, the compound represented by the above formula (1) is useful as a catalyst for producing a polyolefin resin for fibers, since two anion structures coordinating a central metal atom are different from each other and contain a specific substituent group in each anion structure.
R 1 is substituted at the 4th to 7th positions as shown below among the substitution positions of indenyl in the above formula (1), preferably substituted at the 4th or 6th position.
R a and R b are preferably phenyl.
R 2 is preferably C 2-10 alkenyl, more preferably C 2-5 alkenyl, more preferably butenyl, most preferably but-3-enyl, to be.
R 3 to R 7 each independently preferably is C 1-10 alkyl, more preferably C 1-5 alkyl, and most preferably methyl.
M represents a central atom of a metallocene compound bonded to two cyclopentadienyls of the above formula (1 is cyclopentadienyl of indenyl). M is preferably titanium, zirconium or hafnium, more preferably zirconium.
With X 1 and X 2 are preferably, each independently fluoro, chloro, bromo, iodo, C 1-10 alkyl, C 2-10 alkenyl, C 6-10 aryl, nitro, amido, C 1- 10 alkylsilyl group, a C 1-10 alkoxy, or C 1-10 sulphonate. More preferably, X 1 and X 2 are chloro.
Representative examples of the compound represented by the formula (1) are as follows:
The present invention also provides a process for the preparation of the compounds as follows:
[Reaction Scheme 1]
(In the above Reaction Scheme 1, R 1 to R 7 , M, X 1 and X 2 are as defined above, and X 3 is halogen)
In the first step of the reaction, the compound represented by Formula 1-1 is reacted with alkyl lithium (preferably, C 1-10 alkyl lithium, more preferably n-butyl lithium) Is prepared. As a solvent for the reaction, toluene can be used.
The second step of the above reaction is a step of reacting the compound represented by Formula 1-2 and the compound represented by Formula 1-3 to prepare a compound represented by Formula 1 according to the present invention. As a solvent for the reaction, toluene can be used.
The present invention also provides a supported catalyst comprising the compound and the carrier.
It is preferable that the carrier has a hydroxyl group and / or a siloxane group having high reactivity on the surface. Examples of such carriers are the dried silica in a high-temperature, silica-alumina, or silica-may be made of magnesia and the like, which typically Na 2 O, K 2 CO 3, BaSO 4, or Mg (NO 3) an oxide of a second, etc. , Carbonate, sulphate or nitrate components.
The carrier is preferably used in a sufficiently dried state before the compound represented by the formula (1) is supported. At this time, the drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 400 to 600 ° C. If the drying temperature of the carrier is less than 200 ° C, moisture is excessively large and the surface moisture reacts with the cocatalyst. When the temperature exceeds 800 ° C, the pores on the surface of the carrier are combined to reduce the surface area. And only the siloxane group is left, and the reaction site with the co-catalyst is reduced, which is not preferable.
In addition, the supported catalyst may further comprise a first co-catalyst and / or a second co-catalyst.
The first cocatalyst can be used as long as it is a cocatalyst used for polymerizing an olefin under a general metallocene catalyst. This first co-catalyst causes a bond to be formed between the hydroxy group and the Group 13 transition metal in the support. Also, the presence of the first co-catalyst only on the surface of the carrier can contribute to securing the intrinsic properties of the present specific catalyst composition without the fouling phenomenon that the polymer particles cling to the reactor wall surface or to each other.
The first co-catalyst may be at least one selected from the group consisting of compounds represented by the following formulas (3) and (4)
(3)
- [Al (R 15 ) -O] a -
[Chemical Formula 4]
D 1 (R 19 ) 3
In this formula,
R < 15 > may be the same or different from each other, and each independently is halogen or C1-20 hydrocarbyl substituted or unsubstituted with halogen, a is an integer of 2 or more,
R < 19 > may be the same or different from each other and are each independently halogen; And a C 1-20 hydrocarbon group substituted with C 1-20 hydrocarbon group, or a halogen,
D 1 is aluminum or boron.
Examples of the compound represented by the general formula (3) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like. A more preferred compound is methylaluminoxane.
Examples of the compound represented by Formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.
The second co-catalyst may control the molecular weight distribution of the polyolefin and may be at least one selected from compounds represented by the following general formulas (5) and (6)
[Chemical Formula 5]
[LH] + [Z (A) 4 ] -
[Chemical Formula 6]
[L] + [Z (A) 4 ] -
In the above formulas (5) and (6)
L are each independently a neutral or cationic Lewis acid,
H are each independently a hydrogen atom,
Z is each independently a boron,
A is each independently an aryl or alkyl group having 6 to 20 carbon atoms in which at least one hydrogen is substituted with halogen, C 1-20 hydrocarbyl, C 1-20 alkoxy, phenoxy, nitrogen, phosphorus, sulfur or an oxygen atom.
Specific examples of the second cocatalyst include trityl tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) Triethylammonium tetrakis (pentafluorophenyl) borate, or tripropylammonium tetrakis (pentafluorophenyl) borate.
The supporting conditions are not particularly limited, and can be carried out in a range well known to those skilled in the art. For example, the reaction can be carried out by appropriately using high-temperature loading and low-temperature loading. Specifically, when the first co-catalyst and / or the second co-catalyst are supported on the carrier, the temperature can be 25 to 100 ° C. At this time, the carrying time of the first co-catalyst and the carrying time of the second co-catalyst can be appropriately adjusted according to the amount of the co-catalyst to be carried. The reaction temperature of the compound represented by the formula (1) and the carrier may be from -30 to 150 ° C, preferably from room temperature to 100 ° C, more preferably from 30 to 80 ° C. The supported catalyst can be used as it is by filtration of the reaction solvent or by distillation under reduced pressure, and if necessary, it can be used by a Soxhlet filter with aromatic hydrocarbons such as toluene.
The present invention also provides a process for producing a polyolefin polymer, comprising copolymerizing at least one olefin monomer in the presence of the supported catalyst.
Examples of the olefin monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, , 1-tetradecene, 1-hexadecene, and 1-aidocene may be used.
When the olefin monomer is copolymerized, the metallocene supported catalyst may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms such as isobutane, pentane, hexane, heptane, nonane, decane and isomers thereof, an aromatic hydrocarbon such as toluene and benzene menstruum; Dichloromethane, and a hydrocarbon solvent substituted with a chlorine atom such as chlorobenzene. Preferably, the solvent is treated with a small amount of aluminum to remove a small amount of water, air, or the like acting as a catalyst poison.
The polymerization of the olefinic monomer may be carried out using a single reactor selected from the group consisting of a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, and a solution reactor, or using two or more of the same or different reactors to schedule the olefin monomer And can be carried out according to a conventional method.
The polymerization temperature at the time of polymerization of the olefin-based monomer is preferably 25 to 500 ° C, more preferably 25 to 200 ° C, and even more preferably 50 to 150 ° C. The polymerization pressure is preferably 1 to 100 Kgf / cm2, more preferably 1 to 70 Kgf / cm2, most preferably 5 to 50 Kgf / cm2.
The polyolefin polymer produced according to the present invention is excellent in processability, has excellent properties such as high elongation and high strength, and can be used for producing high tensile strength fibers.
The present invention also provides a method for producing a fiber comprising a resin composition comprising the polyolefin polymer and a processing step by means of an extruder.
In the method for producing a fiber according to the present invention, the resin composition containing the olefin polymer may include other additives. Specifically, such additives include heat stabilizers, antioxidants, UV absorbers, light stabilizers, metal deactivators, fillers, reinforcing agents, plasticizers, lubricants, emulsifiers, pigments, optical bleaches, flame retardants, antistatic agents and foaming agents. The kind of the additive is not particularly limited, and general additives known in the art can be used.
Further, the present invention can provide an article comprising the fiber. Specific examples of the fiber-containing articles include articles such as monofilament products such as ropes, fishing nets, safety nets, sport nets, etc., tarpaulins such as covers, saddles, hoses, tents, etc., .
The compound represented by formula (1) of the novel structure according to the present invention can be usefully used for producing a polyolefin resin for fibers, and the polyolefin polymer produced by using the same has excellent processability and excellent properties such as high elongation and high strength Can be used to produce high tensile fibers.
Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.
Example One
Step 1) Metallocene Compound precursor synthesis
10 mL (20 mmol) of 2 M 4-MgBr-1-butene was added to 1.67 g (10 mmol) of 4-bromo-2,4-dihydro- After slowly injecting at 0 ° C, the temperature was slowly raised and stirred at 35-40 ° C for 12 hours. After the reaction time was over, the reaction was terminated by adding cold water. The pH was adjusted with aqueous NH 4 Cl solution and the product was extracted with diethylether.
After dissolving the product in 10 mL of toluene, 0.1 g of p-toluenesulfonic acid monohydrate was added and refluxed for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, washed with 2% Na 2 CO 3 and then extracted with diethylether to obtain 4-bromo-3- (but-3-en-1-yl) 3- (but-3-en-1-yl) -1H-indene.
2.27 g (10 mmol) of the above product, 4.18 g (24.73 mmol) of Ph 2 NH and 1.98 g (24.73 mmol) of t-BuOLi were added to dioxane and stirred for 5 minutes. Then, 0.61 g (1.5 mmol) of 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (S-Phos), and bis (dibenzylideneacetone) palladium (0) 2 ) 0.23 g (0.40 mmol) was added and refluxed for 5 hours. After cooling to room temperature, excess methanol was added and stirred for 1 minute and filtered to obtain 1- (but- 1-yl) -N, N-diphenyl-1H-inden-4-amine (1- ≪ / RTI >
1 H NMR (CDCl 3 , 600 MHz): 2.46 - 2.54 (m, 2H); 2.65-2.71 (m, 2H); 2.85 (d, J = 2.02 Hz, 1 H); 5.06 (dd, J = 10.09, 1.83 Hz, 1 H); 5.15 (dd, J = 17.15, 1.74 Hz, 1 H); 5.94-6.04 (m, 1 H), 6.15 (t, J = 1.56 Hz, 1 H); 6.99 (t, J = 7.34 Hz, 2 H); 7.05 (d, J = 7.70 Hz, 1 H); 7.07 (d, J = 8.44 Hz, 4H); 7.22-7.28 (m, 5 H); 7.33 (t, J = 7.61 Hz, 1H).
13 C NMR (CDCl 3, 151 MHz): 27.2; 32.1; 36.9; 114.8; 115.9; 121.8; 122.4; 122.5; 122.6; 123.9; 127.7; 128.2; 129.0; 138.4; 143.4; 147.5; 147.6.
Step 2) Metallocene Compound synthesis
To a solution of 2.05 g (10 mmol) of the metallocene compound 1- (butyl-3-en-1-yl) -N, N-diphenyl-1H-inden-4-amine dissolved in toluene in an argon atmosphere at- After slowly injecting 4 mL (10 mmol) of M n-BuLi, the temperature was slowly raised and stirred at 55 ° C for 12 hours.
Then, the reaction solution was cooled again to -78 占 폚, and then, under argon, 3.33 g (10 mmol) of 1,2,3,4,5-pentamethylcyclopenta- (1,2,3,4,5-pentamethylcyclopenta-2,4-dien-1-yl) zirconium (IV) chloride was slowly added and the temperature was slowly raised. Lt; / RTI > After the stirring was completed, the solution was filtered through a filter with celite, and then about 2/3 of toluene was removed. Thereafter, hexane was added thereto to effect recrystallization, and then filtered again to obtain the target compound.
1 H NMR (C 6 D 6 , 600 MHz): 1.86 (s, 15H); 2.20-2.27 (m, 1 H); 2.28-2.37 (m, 1 H); 2.95-3.06 (m, 1 H); 3.20-3.28 (m, 1 H); 5.03 (dd, J = 10.19, 1.89 Hz, 1 H); 5.10 (dd, J = 17.10, 1.73 Hz, 1 H); 5.32 (d, J = 2.47 Hz, 1 H); 5.45 (d, J = 2.96 Hz, 1 H), 5.83 - 5.92 (m, 1H); 6.96 (t, J = 7.32 Hz, 4H); 7.03-7.06 (m, 1 H); 7.21-7.23 (m, 2H); 7.26-7.29 (m, 5 H); 7.33 (d, J = 8.39 Hz, 1 H).
13 C NMR (C 6 D 6 , 151 MHz): 12.82; 29.24; 34.19; 97.03; 112.31; 115.06; 119.00; 120.80; 124.06; 124.15; 125.94, 126.10; 127.45; 128.68, 129.85; 138.79; 144.65; 148.70.
Step 3) Preparation of Supported Catalyst
The supported catalyst was prepared using the compound prepared in Step 2 above. Specifically, 54.6 mL of 10 wt% methylaluminoxane (MAO) / toluene solution was added to a glass reactor, 10 g of silica was added at 40 ° C., and the reactor was heated to 200 ° C. for 12 hours Lt; / RTI > Thereafter, the temperature was lowered again to 40 ° C, and 0.1 mmol of the compound prepared in the above step 2 was added. After stirring for 2 hours, 1040 mg of N, N-dimethylanilinium tetrakis (pentafluorophenyl) -borate was preliminarily dissolved in 30 mL of toluene, and the solution was then added to the solution and stirred overnight. Thereafter, the toluene layer was separated and removed, and the residual toluene was removed by reducing the pressure at 40 ° C to prepare a supported catalyst.
Example 2
A supported catalyst was prepared in the same manner as in Example 1, except that N, N-dimethylanilinium tetrakis (pentafluorophenyl) -borate was not used in Step 3 of Example 1 above.
Example 3
A supported catalyst was prepared in the same manner as in Example 1 except that 0.15 mmol of the compound prepared in Step 2 of Example 1 was used in Step 3 of Example 1 above.
Comparative Example
A metallocene catalyst represented by the following formulas (a) and (b) (aldrich) was used to prepare a hybrid supported catalyst.
(A)
[Formula b]
Specifically, 54.6 mL of 10 wt% methylaluminoxane (MAO) / toluene solution was added to a glass reactor, 10 g of silica was added at 40 ° C., and the reactor was heated to 200 ° C. for 12 hours Lt; / RTI > Thereafter, the temperature was lowered again to 40 ° C, and 0.1 mmol of the compound represented by the formula a was added. After stirring for 2 hours, 0.1 mmol of the compound represented by formula (b) was added and stirred for 2 hours. Next, 1040 mg of N, N-dimethylanilinium tetrakis (pentafluorophenyl) -borate was preliminarily dissolved in 30 mL of toluene, and then the solution was added thereto and stirred overnight. Thereafter, the toluene layer was separated and removed, and the residual toluene was removed by reducing the pressure at 40 ° C to prepare a supported catalyst.
Experimental Example
The polyethylene was polymerized using a Parr reactor. Specifically, 400 mL of hexane was added to an isolated system filled with argon, 1 g of trimethylaluminum was added to dry the inside of the reactor, and hexane was removed. The reactor was again filled with 400 mL of hexane and 0.5 g of triisobutylaluminum. In a glove box filled with argon, 10 mg of the supported catalyst prepared in Examples 1 to 4 and Comparative Example were put into a reactor and ethylene pressure of 9 bar was prepared at 78 ° C and polymerization was carried out for 1 hour.
The physical properties of the polyethylene produced according to the above were evaluated under the following conditions.
1) Bulk Density (BD): The bulk density (g / mL) of the Bulk Density Measurement System of Ray-Ran Co. was measured.
2) Weight average molecular weight (Mw) and molecular weight distribution (PDI): The number average molecular weight and the weight average molecular weight were measured using a gel permeation chromatography (GPC) at a measurement temperature of 160 캜. The molecular weight distribution was calculated by the ratio of the weight average molecular weight to the number average molecular weight.
3) Number of gels per unit area: A casting film (54 mm × 33 m) for gel analysis was prepared at 190 ° C. using a single screw extruder (Teachline E20T; Dr. Collin) Was measured three times for 10 minutes to calculate the average number of gels.
The results are shown in Table 1 below.
(kgPE / gCat.)
(g / mL)
As shown in Table 1, in Examples 1 to 4 according to the present invention, the molecular weight distribution was narrower and the number of gels per unit area was significantly smaller than that of Comparative Examples. From these results, it can be confirmed that the compound according to the present invention is useful for the production of high strength polyolefin fibers which are excellent in workability and excellent in high elongation and high strength characteristics.
Claims (16)
[Chemical Formula 1]
In this formula,
R 1 is NR a R b ,
R a and R b are phenyl,
R 2 is C 2-20 alkenyl,
R 3 to R 7 are each independently selected from the group consisting of hydrogen, C 1-20 alkyl, C 1-20 alkoxy, C 2-20 alkenyl, C 6-20 aryl, C 7-20 alkylaryl, C 7-20 arylalkyl, C 3-20 cycloalkyl, or C 5-20 heteroaryl,
M is a Group 4 transition metal,
X 1 and X 2 are each independently selected from the group consisting of halogen, C 1-20 alkyl, C 2-20 alkenyl, C 6-20 aryl, nitro, amido, C 1-20 alkylsilyl, C 1-20 alkoxy, C 1-20 sulfonate.
And R < 2 > is butenyl.
compound.
And R < 3 > to R < 7 > are methyl.
compound.
And M is titanium, zirconium or hafnium.
compound.
X < 1 > and X < 2 > are chloro.
compound.
Wherein said compound is < RTI ID = 0.0 >
compound:
Characterized in that the supported catalyst further comprises at least one of a first co-catalyst and a second co-catalyst.
Supported catalyst.
Wherein the first co-catalyst is at least one selected from the group consisting of compounds represented by the following general formulas (3) and (4)
Supported catalyst:
(3)
- [Al (R 15 ) -O] a -
[Chemical Formula 4]
D 1 (R 19 ) 3
In this formula,
R < 15 > may be the same or different from each other, and each independently is halogen or C1-20 hydrocarbyl substituted or unsubstituted with halogen, a is an integer of 2 or more,
R < 19 > may be the same or different from each other and are each independently halogen; And a C 1-20 hydrocarbon group substituted with C 1-20 hydrocarbon group, or a halogen,
D 1 is aluminum or boron.
Wherein the compound represented by the general formula (3) is methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane.
Supported catalyst.
The compound represented by the general formula (4) may be at least one selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- But are not limited to, pentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, Triethyl boron, triisobutyl boron, tripropyl boron or tributyl boron.
Supported catalyst.
Wherein the second co-catalyst is at least one selected from the group consisting of compounds represented by the following general formulas (5) and (6)
Supported catalyst:
[Chemical Formula 5]
[LH] + [Z (A) 4 ] -
[Chemical Formula 6]
[L] + [Z (A) 4 ] -
In the above formulas (5) and (6)
L are each independently a neutral or cationic Lewis acid,
H are each independently a hydrogen atom,
Z is each independently a boron,
A is each independently an aryl or alkyl group having 6 to 20 carbon atoms in which at least one hydrogen is substituted with halogen, C 1-20 hydrocarbyl, C 1-20 alkoxy, phenoxy, nitrogen, phosphorus, sulfur or an oxygen atom.
The second co-catalyst may be selected from the group consisting of triethyltetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) Characterized in that it is tetrakis (pentafluorophenyl) borate or tripropylammonium tetrakis (pentafluorophenyl) borate.
Supported catalyst.
The olefin monomers may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-tetradecene, 1-hexadecene, and 1-aidocene.
Lt; RTI ID = 0.0 > polyolefin < / RTI >
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| KR1020150083651 | 2015-06-12 |
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| KR20160146503A KR20160146503A (en) | 2016-12-21 |
| KR101828929B1 true KR101828929B1 (en) | 2018-02-13 |
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| KR1020160015298A KR101828929B1 (en) | 2015-06-12 | 2016-02-05 | Compound for preparing polyolefin for preparing fiber and supported catalyst comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011012245A1 (en) * | 2009-07-27 | 2011-02-03 | Basell Polyolefine Gmbh | Organometallic transition metal compound, catalyst system and preparation of polyolefins |
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| WO2011012245A1 (en) * | 2009-07-27 | 2011-02-03 | Basell Polyolefine Gmbh | Organometallic transition metal compound, catalyst system and preparation of polyolefins |
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