WO2019103306A1 - Polypropylène et son procédé de préparation - Google Patents

Polypropylène et son procédé de préparation Download PDF

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Publication number
WO2019103306A1
WO2019103306A1 PCT/KR2018/011638 KR2018011638W WO2019103306A1 WO 2019103306 A1 WO2019103306 A1 WO 2019103306A1 KR 2018011638 W KR2018011638 W KR 2018011638W WO 2019103306 A1 WO2019103306 A1 WO 2019103306A1
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Prior art keywords
formula
homopolypropylene
group
halogen
compound
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PCT/KR2018/011638
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English (en)
Korean (ko)
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WO2019103306A8 (fr
Inventor
김태진
채성민
노경섭
정인용
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020180116448A external-priority patent/KR102326791B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201880005191.7A priority Critical patent/CN110099934B/zh
Priority to EP18881653.2A priority patent/EP3546489A4/fr
Priority to CN202211471604.5A priority patent/CN115785313B/zh
Priority to JP2019529231A priority patent/JP6783937B2/ja
Priority to US16/464,871 priority patent/US11384180B2/en
Publication of WO2019103306A1 publication Critical patent/WO2019103306A1/fr
Publication of WO2019103306A8 publication Critical patent/WO2019103306A8/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
    • A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
    • A47L13/16—Cloths; Pads; Sponges
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
    • 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
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
    • 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
    • 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
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4291—Olefin series

Definitions

  • the present invention relates to a polypropylene having a high strength and a low low molecular weight content together with excellent processability and a process for producing the polypropylene.
  • Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, both of which have been developed for their respective characteristics. Since Ziegler - Natta catalyst has been widely applied to existing commercial processes since its invention in the 1950s, it is characterized by a wide molecular weight distribution of the polymer because it is a multi - site catalyst ( 111111 ⁇ - 3 4 6 . , There is a problem that the composition distribution of the comonomer is not uniform and there is a limit in securing desired physical properties.
  • the metallocene catalyst is composed of a combination of a main catalyst, which is a main component of a transition metal compound, and an organometallic compound artificial catalyst,
  • the molecular weight distribution is narrow, the polymer having uniform composition distribution of comonomer is obtained, and the stereoregularity of the polymer, copolymerization characteristics, molecular weight, crystallinity And the like.
  • Homopolypropylene for disposable wiping purpose usually made of Ziegler-Natta catalyst, has the problem of deteriorating physical properties as well as deteriorating workability when the strength is increased or the basis weight is lowered.
  • Disposable wipes made of Ziegler-Natta catalyst are more preferable than homopolypropylene made of a metallocene catalyst Because of the high content of xylene solubles and low molecular weight due to its broad molecular weight distribution, it was unsuitable for use as a detergent because of its soft surface when applied as a scrubber.
  • homopolypropylene satisfying the following conditions:
  • melt index (measured at 230 ⁇ ⁇ under a load of 2.16 kg according to ASTM D1238) 200 to 2000 g / 10 m in
  • a process for producing a homopolypropylene as described above which comprises polymerizing a propylene monomer by introducing hydrogen at 700 to 2500 ppm in the presence of a catalyst composition comprising a compound represented by the following formula Lt; / RTI > 2019/103306 1 »(: 1 ⁇ 1 ⁇ 2018/011638
  • the urine is carbon, silicon or germanium
  • Each of 3 ⁇ 4 and 3 ⁇ 4 is independently halogen
  • Each of 3 ⁇ 4 and 3 ⁇ 4 is independently 0 6-20 aryl substituted with 0 1-20 alkyl
  • Each of 3 ⁇ 4 to 3 ⁇ 4 and 3 ⁇ 4 to 3 ⁇ 4 is independently selected from the group consisting of hydrogen, halogen, 0 1-20 alkyl, 0 2-20 alkenyl, 0 1-20 alkylsilyl, 0 1-20 silylalkyl, 0 1-20 alkoxysilyl, ( ⁇ 20 ether, 0 1-20 silyl ether, 0 1-20 alkoxy, (: 6-20 aryl, 0 7-20 alkylaryl, or 0 7-20 arylalkyl,
  • a resin composition for a nonwoven fabric comprising the above homopolypropylene, and a nonwoven fabric manufactured using the same, more specifically, a nonwoven fabric for washing such as a wool.
  • the homopolypropylene according to the present invention exhibits excellent workability by having a low residual stress ratio and xylene solubles, an optimum range of melt index and a narrow molecular weight distribution, and is excellent in the production of fibers with a thin and uniform thickness and high rigidity 2019/103306 1 »(: 1 ⁇ 1 ⁇ 2018/011638
  • nonwoven fabric It is possible to manufacture a low basis weight nonwoven fabric. In addition, it can give a tougher touch than existing products, and it can realize excellent toughness that is not torn easily even at high strength. Accordingly, it can be useful for the production of nonwoven fabrics requiring high surface roughness and high surface roughness, in particular, cleaning nonwoven fabrics such as scrubbers.
  • the present invention relates to a disposable scrubber made of a conventional Ziegler-Natta catalyst, which is prepared by polymerizing propylenes under the conditions of hydrogen introduction of a controlled amount using a metallocene catalyst described below to prepare a homopolypropylene
  • the produced homopolypropylene has a narrow molecular weight distribution and a low residual stress so that it is possible to produce fibers having a small thickness and uniformity, and as a result, it is possible to produce a low basis weight nonwoven fabric having high rigidity.
  • the homopolypropylene to be produced has a narrow molecular weight distribution and low low molecular weight content due to low xylene solubles, which can provide a rough feeling on the surface, and as a result, it improves the cleaning effect when applied to a cleaning nonwoven fabric .
  • the nonwoven fabric can be produced by only primary processing, thereby improving the processability.
  • the homopolypropylene according to one embodiment of the present invention meets the following conditions:
  • the homopolypropylene according to one embodiment of the present invention 230 ° (according to the 1238: is from 2.161 3 ⁇ 4 a melt index (, 1 1 ⁇ adenomyosis ⁇ measured under a load of 200 to 2001 ⁇ 2 / 10 1 11. 1) can be controlled according to the amount of hydrogen supplied during the polymerization process.
  • the homopolypropylene according to the present invention has the above-mentioned range in consideration of the above-mentioned requirements to physical properties, thereby improving the strength of the radioactive and non- . In a particularly as the processing of the nonwoven fabric using a homopolypropylene 3 ⁇ 4!
  • the homopolypropylene may have a ratio of 220 to 1500/10 11 .
  • the molecular weight distribution is determined by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) using gel permeation chromatography (GPC) (Mw / Mn). Specifically, it can be measured using a Waters PL-GPC220 instrument using a Polymer Laborator ies PLgel MIX-B 300 mm length column. At this time, the evaluation temperature is 160 ° C, 1,2,4-trichlorobenzene is used as a solvent, and the flow rate is 1 mL / min. The sample is prepared at a concentration of 10 mg / 10 mL, and then supplied in an amount of 200 uL.
  • GPC gel permeation chromatography
  • Mw and Mn are derived using a calibration curve formed using polystyrene standards.
  • the molecular weight (g / mol) of the polystyrene standard product was 9 kinds of 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000.
  • homopolypropylene according to one embodiment of the invention has a low residual stress ratio of 0.05% or less, together with MI and MWD as described above.
  • the residual stress ratio can be determined by a rheological property test under an environment similar to that of the nonwoven fabric manufacturing process.
  • the stress relaxation test is performed to apply a large strain to the homopolypropylene, From the residual stress value measured at this time, it can be calculated according to the following equation ( 1 ).
  • Residual stress ratio (RSi / RSo) x 100
  • R3 ⁇ 4 is the homopolypropylene under 235 ° C
  • RS Q is a homopolypropylene Represents the residual stress immediately after application of 200% strain (for example, at a point of time less than 0.05 seconds).
  • R? Represents the residual stress within about 1.5 seconds (for example, at a time point (ti) between 0.05 second and 1.50 second) after the toe under the condition of the same RSo.
  • the to can be selected from 0.01 second, 0.015 second, or 0.02 second, or 0.025 second, or 0.03 second, or 0.035 second, or 0.04 second, or 0.045 second.
  • U represents 3 ⁇ 4.05 seconds, or 0.10 seconds, or 0.20 seconds, or 0.30 seconds, or 0.40 seconds, or 0.50 seconds, or 0.60 seconds, or 0.70 seconds, or 0.80 seconds, or 0.90 seconds, Or 1.00 seconds, or 1.10 seconds, or 1.20 seconds, or 1.30 seconds, or 1.40 seconds, or 1.50 seconds.
  • the residual stress ratio of the homopolypropylene is measured under an environment (for example, 235 ° C) similar to the process conditions for performing the melt blowing in the production of the nonwoven fabric.
  • the temperature of 235 ° C corresponds to a temperature suitable for completely melting the homopolypropylene composition to perform melt blowing.
  • the nonwoven fabric is usually produced by spinning into fibers in the molten state of the resin and performing a drawing process in a semi-molten state through cooling. At this time, when the ratio of the residual stress according to Equation (1) is higher than 0.05%, it shows a high resistance to deformation, so that it is difficult to manufacture a fiber having a small thickness but uniformity because of poor radioactivity in the spinning process.
  • the homopolypropylene according to the present invention has a low residual Since it has a stress ratio, it is possible to produce a fiber having a small thickness and uniformity, and it is possible to manufacture a low basis weight nonwoven fabric with high rigidity with excellent processability.
  • the residual stress ratio of the homopolypropylene may be more specifically from 0.005 to 0.05%, more specifically from 0.005 to 0.03%, or from 0.02 to 0.03%, in consideration of the improvement of the fiber workability by the residual stress ratio control.
  • the homopolypropylene exhibits a tacticity as high as 1.0% by weight or less of xylene solubles (Xs).
  • the xylene-soluble fraction is obtained by dissolving homopolypropylene in xylene, determining the content (% by weight) of the polymer soluble in the cooled xylene determined by crystallizing the insoluble portion from the cooling solution, Contains a polymer chain of stereoregularity. Accordingly, the lower the content of the xylene-soluble fraction, the higher the stereoregularity.
  • the homopolypropylene according to one embodiment of the present invention has such a high stereoregularity that it can exhibit excellent rigidity in the production of a nonwoven fabric.
  • the content of the xylene-soluble fraction of the homopolypropylene may be more specifically 0.5 to 1.0% by weight, and more particularly 0.6 to 0.7% by weight.
  • the xylene-soluble fraction was prepared by adding xylene to a homopolypropylene sample, heating it at 135 ° C for 1 hour, cooling it for 30 minutes, pretreating it, min at a low flow rate (f low rate) for 4 hours and the baseline of RI (Reflect ive Index), DP (Pressure across middle of bridge) and IP (inlet pressure through bridge top to bottom) base l ine) is stabilized, the concentration can be measured by plotting the concentration of the pretreated sample and the amount of the injection, and then measuring the peak area.
  • the melting point can be measured using a differential scanning calorimeter (DSC). Specifically, the temperature of the homopolypropylene was increased to 200 ° C, held at that temperature for 5 minutes, then lowered to 30 ° C, and then the temperature was increased to obtain DSCCDi ferent i al Scanning Calorimeter, TA The melting point of the top of the curve can be measured. In this case, the temperature rise and fall rates are respectively 10 ° C / min, and the melting point is the result measured in the second rise of the temperature.
  • DSC differential scanning calorimeter
  • the homopolypropylene according to one embodiment of the invention having such physical properties as described above is characterized in that in the presence of a catalyst composition comprising a compound of the formula (1) as a catalytically active component, hydrogen is added to the propylene monomer in an amount of from 700 to 250, And then polymerizing the propylene monomer.
  • a catalyst composition comprising a compound of the formula (1) as a catalytically active component
  • Each of 3 ⁇ 4 and 3 ⁇ 4 is independently halogen
  • RTI ID 0.0 &gt
  • R3 &lt / RTI > are each independently 0 3-20 aryl
  • To 3 ⁇ 4 3 ⁇ 4, and to 3 ⁇ 4 3 ⁇ 4 are each independently hydrogen, halogen, alkyl, 0 1-20, 0 2-20 alkenyl, alkylsilyl, 0 1-20 alkyl silyl, 0 1-20 alkoxysilyl group, an ether 20, 0 1-20 silyl ether, 0-20 alkoxy, 0 6-20 aryl, 0 7-20 alkylaryl, or 0 7-20 arylalkyl,
  • Halogen (1 1 ⁇ 2 1 (3 ⁇ 4 below) is fluorine ⁇ ) may be, chlorine (a), bromine (H), or iodine (I).
  • the 0 1-20 alkyl group may be a straight chain, branched chain or cyclic alkyl group. Specifically, the 0 1-20 alkyl group may be a 0 1-15 straight-chain alkyl group; 0 1-10 straight chain alkyl group; 0 1-5 straight-chain alkyl group; A C3-20 branched or cyclic alkyl group; 3 ⁇ 4 15- branched or cyclic alkyl group; Or a 0 3 -10 branched or cyclic alkyl group.
  • the -20 alkyl group is preferably a methyl group, an ethyl group, an 11 -propyl group, - propyl group, 11- butyl group, A butyl group, a 7-butylbutyl group, an 11 -pentyl group, - pentyl group or cyclic nucleus group and the like.
  • the 0 2 -20 alkenyl group may be a straight chain, branched chain or cyclic alkenyl group.
  • Specific examples of the 0 2 -20 alkenyl group include 0 2 -20 straight chain alkenyl groups, 02-10 straight chain alkenyl groups, 0 2 -5 straight chain alkenyl groups, 0 3-20 branched chain alkenyl groups, 0 3-15 branched chain alkenyl groups, ( 3) a branched alkenyl group of 3 to 10 carbon atoms, or a cyclic alkenyl group of 1 (3). More specifically, the 0 2 -20 alkenyl group may be an ethenyl group, a propenyl group, a butenyl group, a pentenyl group or a cyclohexenyl group.
  • 0 6-30 Aryl can mean monocyclic, bicyclic or tricyclic aromatic hydrocarbons. Specifically, 0 6-30 aryl may be phenyl, naphthyl or anthracenyl.
  • 0 7-30 Alkylaryl may mean a substituent wherein at least one hydrogen of the aryl is replaced by an alkyl.
  • 0 7-30 alkylaryl is methylphenyl, ethylphenyl,
  • 0 7 -30 arylalkyl may mean a substituent wherein at least one of the hydrogens of the alkyl is substituted by aryl.
  • the 0 7 -30 arylalkyl may be a benzyl group, a phenylpropyl group, or a phenylhexyl group.
  • the catalyst composition used in the preparation of homopolypropylene according to one embodiment of the present invention includes the compound of Formula 1 as a single catalyst. Accordingly, the molecular weight distribution can be significantly narrowed as compared with the homopolypropylene produced in the past when two or more catalysts are used in combination.
  • the compound of formula (1) is a bridge group connecting two ligands including an indenyl group, and includes a bivalent functional group that is substituted with the same alkyl group having 2 or more carbon atoms, thereby increasing the atom size and increasing the usable angle
  • the monomer is easily accessible and can exhibit better catalytic activity.
  • both of the two indenyl groups as the ligand are substituted with the methyl group at the 2-position, and the 4-position 3 ⁇ 4 and R 5) include the alkyl-substituted aryl group, so that the induction effect It can exhibit better catalytic activity than decomposition.
  • the compound of formula (1) contains zirconium (Zr) as a central metal, thereby having more orbitals capable of accepting electrons as compared with the case of containing other Group 14 elements such as Hf and the like, And as a result, it is possible to exhibit a better catalytic activity improving effect.
  • Ri and 3 ⁇ 4 in the above formula (1) may each independently be a Ce-12 aryl group substituted with Ci-io alkyl, and more specifically, tert-butyl 2019/103306 1 »(: 1 ⁇ 1 ⁇ 2018/011638
  • a phenyl group substituted with 0 3-6 branched alkyl groups such as phenyl.
  • the substitution position of the alkyl group for the phenyl group is 3 ⁇ 4 or 1? 5 position and Position 4 corresponding to the position.
  • Y 2 and Y 3 , and Y 3 and Z 4 each independently may be hydrogen, and each of 3 ⁇ 4 and 3 ⁇ 4 may be chloro.
  • the show may be silicon (), and the substituents of the show are the same in that the solubility is increased to improve the carrying efficiency and may be a 0 2 -10 alkyl group, Specifically 0 2 -4 straight chain alkyl groups, more particularly each ethyl group.
  • the compound of formula (1) can be synthesized by applying known reactions, and a more detailed synthesis method can be referred to the following production examples.
  • the compound of Formula 1 may be used as a single component or may be used in the form of a supported catalyst supported on a support.
  • a carrier having a hydroxyl group or a siloxane group having high reactivity on the surface can be used, and a carrier dried and having moisture removed on its surface can be used.
  • the dried silica in a high-temperature, silica-alumina, and silica _ magnesia and the like may be used, all of which are typically ⁇ 20, 3 ⁇ 4 ⁇ 3, 3 ⁇ 4 et 4, and 3 ⁇ 4 word 03) an oxide of 2, such as carbonate, sulfate , And nitrate components.
  • the temperature at which the carrier is dried may be from 200 to 8001:
  • the drying temperature is excessively high, the pores on the surface of the carrier are aggregated to decrease the surface area. Also, the hydroxyl groups on the surface may be abolished, and only the siloxane group may remain, thus reducing the reaction site with the cocatalyst .
  • the hydroxyl groups on the surface may be abolished, and only the siloxane group may remain, thus reducing the reaction site with the cocatalyst .
  • the amount of the hydroxy group on the surface of the carrier can be controlled by the preparation method and conditions of the carrier or by drying conditions such as temperature, time, vacuum or spray drying. If the amount of the hydroxyl group is too low, the site of reaction with the co-catalyst is small.
  • the weight ratio of the compound of Formula 1 to the carrier may be 1: 1 to 1: 100.
  • the carrier and the compound of Formula (1) are contained at the above weight ratio, they exhibit appropriate supported catalyst activity, which can be advantageous in terms of maintaining the activity of the catalyst and economical efficiency. More specifically, the weight ratio of the compound of formula (I) to the carrier may be from 1:10 to 1:30, more specifically from 1:15 to 1:20.
  • the catalyst composition may further include a cocatalyst in terms of improving the activity and the process stability.
  • the promoter may include at least one compound represented by the following general formula (2), (3) or (4).
  • 1 < / RTI &gt may be the same or different from each other and are each independently selected from the group consisting of halogen; 0 1 to 20 hydrocarbons; Or a hydrocarbon substituted with halogen;
  • 1 is aluminum or boron
  • the seedlings are neutral or cationic Lewis bases
  • 0 are the same or differ from each other, and each independently represent a hydrogen atom is at least one halogen, - a second ⁇ substituted hydrocarbon, alkoxy or phenoxy, or in or unsubstituted aryl group or (2 ⁇ alkyl group.
  • Examples of the compound represented by Formula 2 include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and more specifically, methylaluminoxane.
  • Examples of the compound represented by the general formula (3) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-butylaluminum, tricyclopentylaluminum, tri Tri-n-butylaluminum, tri-n-butylaluminum, pentylaluminum, triisopentylaluminum, triunylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri- 1 -tolylaluminum, dimethylaluminum methoxide, , Triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more specifically may be selected from trimethylalumin
  • Examples of the compound represented by the formula (4) include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, 2019/103306 1 »(: 1 ⁇ 1 ⁇ 2018/011638
  • Tributylammonium tetrapentafluorophenylboron Tributylammonium tetrapentafluorophenylboron, ratiometric diethylanilinium tetraphenylboron, Diethylanilinium tetrapentafluorophenylboron,
  • the weight ratio of the compound of Formula 1 to the cocatalyst may be 1: 1 to 1:20.
  • the catalyst exhibits a proper supported catalyst activity, which is advantageous in view of maintaining the activity of the catalyst and economical efficiency. More specifically, the weight ratio of the compound of formula (I) to the co-catalyst may be from 1: 5 to 1:20, more specifically from 1: 5 to 1:15 2019/103306 1 »(: 1 ⁇ 1 ⁇ 2018/011638
  • the catalyst composition contains both the carrier and the cocatalyst
  • the catalyst composition includes a step of supporting a promoter compound on a support, and a step of supporting the compound represented by the formula 1 on the support
  • the carrying order of the cocatalyst and the compound of formula (1) may be varied as required.
  • hydrocarbon solvents such as pentane, nucleic acid, heptane and the like, or aromatic solvents such as benzene, toluene and the like may be used as a reaction solvent in the preparation of the catalyst composition.
  • the polymerization process can be carried out by contacting the propylene polymer with the catalyst composition containing the compound represented by the formula (1) under hydrogen gas.
  • the hydrogen gas preferably has a mass ratio
  • the molecular weight distribution and the fluidity of the homopolypropylene composition can be controlled within a desired range by controlling the amount of the hydrogen gas used while exhibiting sufficient catalytic activity and thus the homopropylene polymer having appropriate physical properties can be prepared have. If the amount of the hydrogen gas is less than 700, 1 of the produced homopolypropylene may be significantly lowered and the workability may be deteriorated. When the amount of the hydrogen gas is less than 700%, the strength and roughness characteristics of the nonwoven fabric may be lowered . More specifically, the hydrogen gas is 700 And above, or 1503 ⁇ 4 Thyssen 11 or more, or more than 1750, 2503 ⁇ 4) 1 or less Fe, or 2003 ⁇ 4) may be added in an amount up.
  • the polymerization process can be performed by a continuous polymerization process, and various polymerization processes known as polymerization of olefin monomers such as continuous solution polymerization process, bulk polymerization process, suspension polymerization process, slurry polymerization process or emulsion polymerization process are employed .
  • various polymerization processes known as polymerization of olefin monomers such as continuous solution polymerization process, bulk polymerization process, suspension polymerization process, slurry polymerization process or emulsion polymerization process are employed .
  • the polymerization reaction may also be carried out at a temperature of from about 40 to 110 Or about 60 to 100 I: it may be carried out under a pressure of: the temperature and from about 1 to 100 1 3 ⁇ 4 ⁇ .
  • the catalyst may be added in a dissolved or diluted state in a solvent such as pentane, nucleic acid, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene and the like.
  • the homopolypropylene according to one embodiment of the present invention produced by the above production method has an optimum range and a narrow molecular weight distribution together with a low residual stress ratio and xylene solubles, It can be manufactured, and it is possible not only to give rough feeling to the existing product but also to realize excellent toughness which is not torn easily with high strength. Accordingly, it can be particularly useful for the production of nonwoven fabrics requiring high surface roughness and high surface roughness, specifically, cleaning nonwoven fabrics such as scrubbers.
  • a resin composition for a nonwoven fabric including the homopolypropylene and a nonwoven fabric produced using the same.
  • the nonwoven fabric may be a nonwoven fabric for washing such as a scrubbing brush, more specifically, a disposable wipe or the like.
  • the resin composition for a nonwoven fabric and the nonwoven fabric may be produced by a conventional method, except that the homopolypropylene is used. Best Mode for Carrying Out the Invention
  • preferred embodiments are described to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention, and the present invention is not limited to the following examples.
  • Step 3 of Preparation Example 1 The procedure of Step 3 of Preparation Example 1 was repeated except that the compound (I) having the following structure was used instead of the transition metal compound prepared in Step 2 of Preparation Example 1 to prepare a silica-supported metallocene catalyst . 2019/103306 1 »(: 1/10 ⁇ 018/011638
  • Example 1 Specific reaction conditions for the polymerization process are shown in Table 1 below. Homopolypropylene was prepared through such polymerization process. Examples 2 to 5
  • Homo propylene was prepared in the same manner as in Example 1 except that the silica-supported metallocene catalyst prepared in Preparation Example 5 was used and the conditions were set forth in Table 1 below.
  • MI Melt Index
  • Xylene Soluble (wt.%): Xylenes were added to each homopolypropylene sample, heated at 135 ° C for 1 hour, cooled for 30 minutes, and pretreated. The injector was flown for 4 hours at a flow rate of 1 mL / min on an OminiSec (Viscotek FIPA) instrument, and the injected oxygen was injected through the RI (Refract ive Index), DP (Pressure across middle bridge) to bottom of the sample was stabilized, the concentration and injection amount of the pretreated sample were written and measured, and then the peak area was calculated.
  • RI Refract ive Index
  • DP Pressure across middle bridge
  • the temperature of the homopolypropylene to be measured was increased to 200 ° C., maintained at that temperature for 5 minutes, then decreased to 30 ° C., and the temperature was again increased to obtain a DSC (Di f ferent ial Scanning Calorimeter, The top of the curve was the melting point. At this time, the rate of rise and fall of the temperature was 10 ° C / min, and the melting point was determined in a period in which the second temperature rises.
  • Mw and Mn values were derived using a calibration curve formed using polystyrene standards.
  • the molecular weight (g / mol) of the polystyrene standard product was 9 kinds of 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10, 000,000.
  • DHR Discovery Hybrid Rheometer
  • Residual stress ratio (Y) (RSi / RS 0) * 100
  • Equation 1 RSo is a residual stress at 200% strain on the sample fall 0.02 seconds (t Q) was under 235 ° C, R3 ⁇ 4 is 1.00 seconds was added to the 200% strain on the sample under 235 ° C () Is the residual stress.
  • the homopolypropylene of Examples 1 to 5 exhibited remarkably reduced xylene solubles and residual stress ratio as compared with the homopolypropylene of Comparative Example 1 produced using the Ziegler-Natta catalyst, and the molecular weight distribution It was remarkably narrow.
  • a spunbonded nonwoven fabric was produced by performing a melt blowing process using the homopolypropylene-containing resin composition according to the above Examples and Comparative Examples.
  • homopolypropylene according to Examples and Comparative Examples was extruded using a 25 mm twin-screw extruder, 2000 ppm of Irganox 1010 TM as an antioxidant,
  • a master batch containing 2000 ppm of Irgafos 168 TM was prepared and then pelletized. Subsequently, the molten masterbatch composition was fed to a melt pump (65 rpm) using a 31 mm Brabender conical twin screw extruder, and then extruded through a discharge port (10 discharge ports 8 m) and a 25 cm wide discharge port Except for the fact that it was supplied to the meltblowing die, 4364 of the Naval Research Laboratories ies, publ i shed May 25, 1954 ent i t led "Manufacture of Superfine Organic Fiber" by Wente, Van.
  • the master batch pellets were extruded into a microfiber web by a process similar to that described in A. Boone, C. D., and Fluharty, E.
  • the melt temperature was 235 ° C
  • the screw speed was 120 rpm
  • the weight of the manufactured nonwoven fabric was measured, and the weight of the nonwoven fabric per unit area was measured.
  • nonwoven fabric was checked for the occurrence of single yarns, and the processability of the nonwoven fabric was evaluated according to the following criteria.
  • the roughness of the nonwoven fabric was measured by ten blind panel evaluations and evaluated according to the following criteria:
  • Comparative Example 1 produced using the Ziegler-Natta catalyst, the workability was poor, and the strength and roughness characteristics were significantly lowered than in Examples 1 to 5.
  • blending and secondary processing with an additive for increasing the roughness property are indispensable in order to manufacture the nonwoven fabric for cleaning using the homopolypropylene produced according to Comparative Example 1.
  • Comparative Examples 2 to 4 using compounds having different structures as the catalytically active material, poor workability was exhibited due to a high residual stress ratio as compared with Example 1 having the same MI, and as a result, web formability (web and the strength was degraded due to poor quality of the film.
  • Comparative Example 5 in which the amount of hydrogen input was excessively low, even when the same catalyst was used, the MI value was lowered to less than 200 g / 10 m < 2 >
  • Comparative Example 6 in which the hydrogen input amount was too high, the degraded roughness characteristics were exhibited due to MI exceeding 2000 g / 10 min, and due to the increase of the high ⁇ D and xylene solubles exceeding 3.3, Compared to the examples.

Abstract

La présente invention concerne un homopolymère de polypropylène ayant une excellente aptitude à la mise en œuvre, une résistance élevée et une faible teneur en molécules de faible masse moléculaire, et son procédé de préparation.
PCT/KR2018/011638 2017-11-27 2018-10-01 Polypropylène et son procédé de préparation WO2019103306A1 (fr)

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CN201880005191.7A CN110099934B (zh) 2017-11-27 2018-10-01 聚丙烯及其制备方法
EP18881653.2A EP3546489A4 (fr) 2017-11-27 2018-10-01 Polypropylène et son procédé de préparation
CN202211471604.5A CN115785313B (zh) 2017-11-27 2018-10-01 聚丙烯及其制备方法
JP2019529231A JP6783937B2 (ja) 2017-11-27 2018-10-01 ポリプロピレンおよびその製造方法
US16/464,871 US11384180B2 (en) 2017-11-27 2018-10-01 Polypropylene and method for preparing the same

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KR20150037652A (ko) * 2013-09-30 2015-04-08 주식회사 엘지화학 폴리프로필렌의 제조방법 및 이로부터 수득되는 폴리프로필렌
KR20150052803A (ko) * 2013-11-06 2015-05-14 주식회사 엘지화학 폴리프로필렌
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See also references of EP3546489A4
WENTE, V. A.BOONE, C. D.FLUHARTY, E. L.: "Report No. 4364", 25 May 1954, NAVAL RESEARCH LABORATORIES, article "Manufacture of Superfine Organic Fibers"

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