WO2019103306A1

WO2019103306A1 - Polypropylene and preparation method therefor

Info

Publication number: WO2019103306A1
Application number: PCT/KR2018/011638
Authority: WO
Inventors: 김태진; 채성민; 노경섭; 정인용
Original assignee: 주식회사 엘지화학
Priority date: 2017-11-27
Filing date: 2018-10-01
Publication date: 2019-05-31
Also published as: WO2019103306A8

Abstract

The present invention provides a homo polypropylene having excellent processability, high strength, and a low amount of low molecular weight molecules, and a preparation method therefor.

Description

2019/103306 1 »(: 1 ^ 1 {2018/011638

Title of the Invention

Polypropylene and its production method

TECHNICAL FIELD

Cross-reference with related application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0159736, dated November 27, 2017, and Korean Patent Application No. 10-2018-0116448, dated September 28, 2018, The entire contents of which are incorporated herein by reference.

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.

BACKGROUND ART [0002]

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.

On the other hand, 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,

According to the single active site characteristic, 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.

In order to compensate for these drawbacks, a method has been proposed in which a polypropylene having a melt index (MI) of 230 g / 10 min produced by a conventional Ziegler-Natta catalyst is blended with an additive to extract a rough feel and a thick fiber, - Natta catalyst and the blended polypropylene composition blended with additives cause poor spinnability and produce uneven fibers, resulting in deterioration of physical properties. In addition, there is a disadvantage that the processing cost is high because it leads to dry blending -> thermal processing -> pel let izing -> second processing -> product Have.

DETAILED DESCRIPTION OF THE INVENTION

[Technical Problem]

Accordingly, it is an object of the present invention to provide a homopolypropylene having a high strength and a low molecular weight content with excellent processability by using a metallocene catalyst having a specific structure instead of a Ziegler-Natta catalyst, and a process for producing the same.

[Technical Solution]

According to one embodiment of the present invention, there is provided homopolypropylene satisfying the following conditions:

i) melt index (measured at 230 占 폚 under a load of 2.16 kg according to ASTM D1238) 200 to 2000 g / 10 m in

i i) Molecular weight distribution 3.3 or less

i i i) Residual stress ratio not more than 0.05%

iv) xylene additive 1.0% by weight or less

According to another embodiment of the present invention, there is provided 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

[Chemical Formula 1]

In Formula 1,

The urine is carbon, silicon or germanium,

Each of ¾ and ¾ is independently halogen,

Each of ¾ and ¾ is independently 0 _6-20 aryl substituted with 0 _1-20 alkyl,

Each of ¾ to ¾ and ¾ to ¾ 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,

And is C2-20 alkyl.

According to another embodiment of the present invention, there is provided 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.

【Effects of the Invention】

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

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.

BEST MODE FOR CARRYING OUT THE INVENTION

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms " comprising, " " comprising, " or " having ", are intended to specify the presence of stated features, steps, Components, or combinations thereof, as a matter of convenience, without departing from the spirit and scope of the invention.

The invention is capable of various modifications and may take various forms, which illustrate specific embodiments and are described in detail below. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention _.

Hereinafter, homopolypropylene according to a specific embodiment of the present invention, a method for producing the homopolypropylene, and the like will be described. 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. In addition, 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 . Also, 2019/103306 1 »(: 1 ^ 1 {2018/011638

Since homopolypropylene does not need to be blended with the additive, the nonwoven fabric can be produced by only primary processing, thereby improving the processability. Specifically, the homopolypropylene according to one embodiment of the present invention meets the following conditions:

0 Melt index 1) 200 to 200/1 (½ ratio measured at 230 ° (at 2.161 _¾ load) according to 1238

1 1) Molecular weight distribution 3.3

0 Residual stress ratio 0.05% or less

) Xylene content 1.0 wt% or less More specifically, the homopolypropylene according to one embodiment of the present invention

230 ° (according to the 1238: is from 2.161 _¾ a melt index (, _{1 1}比adenomyosis幻measured under a load of 200 to 200½ / 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 ¾! 1 is 200 g / 10 ^ 1111, and is less than if the possibility that the workability by processing pressure rises decrease, 2000 _§ / 10 ₁₁₁ if it exceeds 111, the nonwoven fabric to be produced It is difficult to realize high strength in In the case of using a Ziegler-Natta catalyst in order to produce polypropylene having the above-mentioned range of values, a high content of hydrogen should be added in the polymerization step, but by using a catalyst containing a metallocene compound as described later Since a relatively low content of hydrogen can be introduced, there is an advantage that the activity control is easy and the process stability is enhanced. Considering that the radioactive and nonwoven fabric strength improving effect according to the attached control is excellent, the homopolypropylene may have a ratio of 220 to 1500/10 ₁₁ . In addition, the homopolypropylene according to one embodiment of the present invention has a narrow molecular weight distribution (? 0 = 1/1?) Of 3.3 or less as described above. Such narrow By having a molecular weight distribution, excellent rigidity can be exhibited in the production of nonwoven fabric. More specifically, the homopolypropylene may be 1.5 to 3.3, more specifically 2.5 to 3.3.

Meanwhile, in the present invention, the molecular weight distribution (MWD) 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. Values of Mw and Mn are derived using a calibration curve formed using polystyrene standards. In this case, 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. In addition, 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 ).

[Equation 1]

Residual stress ratio = (RSi / RSo) x 100

In Equation 1, R¾ is the homopolypropylene under 235 ^° C

The residual stress at a certain point (to) of less than 0.05 seconds after the strain of 200% is applied and the residual stress at a certain point of time (h) between 0.05 seconds and 1.50 seconds after applying 200% strain to homopolypropylene ^at 235 ). &Lt; / RTI > Also, in the above formula (1), 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). In the above equation (1), 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. Specifically, in Equation (1), 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. In the above equation (1), U represents ¾.05 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. Preferably, in order to easily assure effective data in the measurement of the residual stress, it is advantageous that in the above equation (1), to is 0.02 sec and silver is 1.00 sec. 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. In addition, since the single yarn occurrence rate is high, the process time is shortened due to the occurrence of single yarn during the fiber production process, resulting in deterioration in processability and it is difficult to carry out the continuous spinning process. In addition, since the web forming ion is poor, there is a fear of a decrease in strength. On the other hand, 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. In addition, the homopolypropylene exhibits a tacticity as high as 1.0% by weight or less of xylene solubles (Xs).

In the present invention, 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. Considering that the improvement effect of the xylene-soluble fraction control is excellent, 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. In the present invention, 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. Further, in addition to the aforementioned MI, MWD, residual stress ratio, and xylene loading conditions, the homopolypropylene has a melt index of 150 to 155 ° C, more specifically, Lt; RTI ID = 0.0 > 154 C < / RTI > When Tm is within the above range, excellent radioactivity and productivity can be exhibited.

In the present invention, 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. 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.

[Chemical Formula 1]

In Formula 1,

Shows are carbon, silicon or germanium, 2019/103306 1 »(: 1 ^ 1 {2018/011638

Each of ¾ and ¾ is independently halogen,

And < RTI ID = 0.0 > _R3 < / RTI > are each independently 0 _3-20 aryl,

To ¾ ¾, and to ¾ ¾ 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,

_{Lt; /} RTI > Unless defined otherwise herein, the following terms may be defined as follows.

Halogen (1 _½ 1 _(¾ below) is fluorine作) 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; ¾ _15- branched or cyclic alkyl group; Or a 0 ₃ -10 branched or cyclic alkyl group. More specifically, 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. Specifically, 0 _7-30 alkylaryl is methylphenyl, ethylphenyl,

Or cyclohexyl phenyl.

0 ₇ -30 arylalkyl may mean a substituent wherein at least one of the hydrogens of the alkyl is substituted by aryl. Specifically, 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. Further, 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. In addition, both of the two indenyl groups as the ligand are substituted with the methyl group at the 2-position, and the 4-position ¾ and R ₅₎ include the alkyl-substituted aryl group, so that the induction effect It can exhibit better catalytic activity than decomposition. Further, 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. More specifically, Ri and ¾ 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

_Or 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 ¾ or 1? ₅ position and

Position 4 corresponding to the position. In the above formula (1), Y ₂ and Y ₃ , and Y ₃ and Z 4 each independently may be hydrogen, and each of ¾ and ¾ may be chloro. In the above formula (1), 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. By having the same alkyl group as the substituent for the show of the bridge group, if the substituent for the element of the conventional bridge group is a methyl group having 1 carbon atom, solubility in the preparation of the supported catalyst is poor and the problem of poor supporting reaction can be solved. Representative examples of the compound represented by the above formula (1) are as follows:

\ ¥ 0 2019/103306 1/10/10 Public 018/011638

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.

As the carrier, 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. For example, the dried silica in a high-temperature, silica-alumina, and silica _ magnesia and the like may be used, all of which are typically此_20, ¾期_{3, ¾} et _4, and ¾ 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:

When the temperature is low, the amount of water remaining in the carrier is too high, 2019/103306 1 »(: 1 ^ 1 {2018/011638

If 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 . In turn may be a hydroxyl group amount of ₁₀ days for the 1 / 0.1 to 10 ^ _0, 1, or 0.5 to ₅₁ of the support surface. 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. If the amount of the hydroxyl group is excessively large, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. When the compound of Formula 1 is supported on a carrier, the weight ratio of the compound of Formula 1 to the carrier may be 1: 1 to 1: 100. When 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. In addition to the compound of formula (1) and the carrier, 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).

(2)

_ [Show 1 (¾ ₁₎ -0] _{111 In the} above formula 2,

Which may be the same or different, each independently halogen; € 1 -

₂₀ hydrocarbons; Or a hydrocarbon substituted with halogen;

Is an integer of 2 or more;

(3)

1 (¾ ₂ ) ₃

In Formula 3, 2019/103306 1 »(: 1 ^ 1 {2018/011638

1 < / RTI > 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;

[Chemical Formula 4]

In Formula 4,

The seedlings are neutral or cationic Lewis bases;

II is a hydrogen atom;

1 is a Group 13 element;

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 ᄋ 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 trimethylaluminum, triethylaluminum, and triisobutylaluminum. Examples of the compound represented by the formula (4) include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, 2019/103306 1 »(: 1 ^ 1 {2018/011638

Trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (tolyl) boron, trimethyl ammonium tetra _(0,1) - dimethylphenyl) boron, tri-butyl ammonium tetra (high-to triple Methylphenyl) boron, trimethylammoniumtetra (I) -trifluoromethylphenyl) boron,

Tributylammonium tetrapentafluorophenylboron, ratiometric diethylanilinium tetraphenylboron,

Diethylanilinium tetrapentafluorophenylboron,

Tetrabutylammonium tetraphenylborate, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tri Propylammonium tetraphenyl aluminum, trimethylammonium tetra (tolyl) aluminum, tripropylammonium tetra (I) -tolyl) aluminum, triethylammonium tetra (◦ _! ) -Dimethylphenyl) aluminum, tributylammoniumtetra (trifluoromethylphenyl) aluminum, trimethylammoniumtetra (trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, ratio-diethylanilinium Tetraphenyl aluminum,

Diethylanilinium tetrapentafluorophenyl aluminum,

Diethylammonium tetrapentatetraphenyl aluminum,

Triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra ( _! ) - tolyl) boron, triethyl ammonium tetra _{_(0,!} ) -Dimethylphenyl) boron, tributylammoniumtetra (I) -trifluoromethylphenyl) boron, triphenylcarboniumtetra (trifluoromethylphenyl) boron, or triphenylcarbonium tetrapentafluorophenylboron , And mixtures of any one or more of them may be used. When the above-described cocatalyst is further included, the weight ratio of the compound of Formula 1 to the cocatalyst may be 1: 1 to 1:20. When the cocatalyst and the compound of formula (1) are contained in the weight ratio, 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

have. In the case where 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 Wherein the carrying order of the cocatalyst and the compound of formula (1) may be varied as required.

At this time, 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. On the other hand, in the process for producing homopolypropylene according to an embodiment of the present invention, 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.

At this time, the hydrogen gas preferably has a mass ratio

It can be put into the contents of 2500 eggs. 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 150¾ Thyssen ₁₁ or more, or more than 1750, 250¾) ₁ or less Fe, or 200¾) 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 . In particular, it is possible to obtain a uniform molecular weight distribution, 2019/103306 1 »(: 1 ^ 1 {2018/011638

Continuous bulk-slurry polymerization processes may be desirable in the production phase. 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 _¾八. Further, in the polymerization reaction, 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. At this time, by treating the solvent with a small amount of alkylaluminum or the like, a small amount of water or air that can adversely affect the catalyst can be removed in advance. 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. Thus, according to another embodiment of the present invention, there is provided a resin composition for a nonwoven fabric including the homopolypropylene and a nonwoven fabric produced using the same. At this time, 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 Hereinafter, 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.

Production Example 1 Step 1) Preparation of (diethylsilanediyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl) silane

2-methyl-4-tert-butylphenylindene (20.0 g) was dissolved in a toluene / THF volume ratio of 10/1 solution (220 mL) 22.2 g) was slowly added dropwise (in TC, followed by stirring at room temperature for one day). To the resultant mixed solution, diethyldichlorosilane (6.2 g) was slowly added dropwise at -78 ^° C, stirred for about 10 minutes, and then stirred at room temperature for an additional day. Thereafter, water was added to separate the organic phase and the solvent was distilled off under reduced pressure to obtain (diethylsilane-diyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl) silane. Step 2) Preparation of [(diethylsilanediyl) -bis (2-methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride

After dissolving the (diethylsilane-diyl) -bis (2-methyl-4-tert-butylphenylindenyl) silane prepared in the above step 1 in toluene / THF] volume ratio = 5/1 solution (120 mL) , A n-butyllithium solution (2.5 M, nucleic acid solvent, 22.2 g) was slowly added dropwise at -78 ° C and stirred at room temperature for one day. To the resulting reaction solution, a solution prepared by diluting zirconium chloride (8.9 g) in toluene (20 mL) was slowly added dropwise at -78 ° C and stirred at room temperature for one day. As a result, the solvent in the resulting reaction solution was removed under reduced pressure, dichloromethane was added thereto, and the mixture was filtered, and the filtrate was distilled off under reduced pressure. (2-methyl-4- (4-tert-butylphenyl) indenyl)] zirconium dichloride (10.0 g) was obtained by recrystallization using toluene and a nucleic acid to obtain a high purity rac- [(diethylsilane-diyl) -bis lg, a yield of 34%, and a weight ratio of rac: meso = 20: 1).

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Step 3) Preparation of the supported catalyst

3 I The reactor was charged with 100 parts by weight of silica and 10% by weight of methylaluminoxane solution (670 g, solvent: toluene) and reacted at 90 ° for 24 hours. After completion of the reaction, when the precipitation was completed, the upper layer solution was removed, and the remaining reaction product was washed twice with toluene. As for the metallocene compound (- A Ansari prepared in step 2: [(diethyl silane-diyl) -bis (2-methyl-4- (4 Ah _{6-butyl-phenyl)} indenyl)] zirconium dichloride 5.8 was diluted in 500 ml of toluene, added to the reactor, and reacted at 70 ° C for 5 hours. After completion of the reaction, the upper layer solution was removed, and the remaining reaction product was washed with toluene, washed again with nucleic acid, and vacuum-dried to obtain 150 _실 of a silica-supported metallocene catalyst in the form of solid particles. Production Example 2

(2-ethyl-4- (4'-tert-butylphenyl) indenyl) (2-methyl-4- (4 ' Ara卜-butylphenyl) indenyl) zirconium dichloride (a slow _{_{1 311 (1 1 (2- 61}} ± 7 1-4- (4'- butyl-phenyl) indenyl) zirconium di chloride) was used in place of the tert-butyl-

1, to thereby produce a silica-supported metallocene catalyst. Production Example 3

(2-methylindenyl) zirconium dichloride instead of the transition metal compound prepared in Step 2 of Preparation Example 1 (2-methylindenyl (2-methylindenyl) zirconium dichloride ) zi rconium dichloride) was used instead of zirconium dichloride, to thereby produce a silica-supported metallocene catalyst. Production Example 4

Dimethylsilanediylbis (2-methyl-4- (4-tert-butylphenyl) indenyl) zirconium dichloride was used instead of the transition metal compound prepared in Step 2 of Preparation Example 1, methyl-4- (4-tert-butylphenyl) indenyl) zirconium di chloride was used as a catalyst, to prepare a silica-supported metallocene catalyst. Production Example 5

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 公 018/011638

Example 1

Bulk-slurry polymerization of propylenes was carried out in the presence of the silica-supported metallocene catalyst prepared in Preparation Example 1, using two continuous loop reactors.

At this time, triethylaluminum (grains) and hydrogen gas were charged by the pumps in the amounts shown in the following Table 1, and the amount of the supported catalyst prepared in Production Example 1 for bulk-slurry polymerization was adjusted to 30 wt% Oil and grease mixed with mud catalyst. The temperature of the reactor is 70 (its production per hour is approximately

Respectively.

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 propylenes were prepared in the same manner as in Example 1, except that the conditions were as shown in Table 1 below. Comparative Example 1 2019/103306 1 »(: 1 ^ 1 {2018/011638

A 1 / ^ homopolypropylene was used 910 ^® (1石Chemical Co., Ltd.) commercially available. Comparative Examples 2 to 4

Except that the reaction was carried out under the conditions described in the following Table 1,

1 to prepare homopropyltethene. Comparative Example 5

Homopolypropene was prepared in the same manner as in Example 1, except that hydrogen was added in an amount of 50). Comparative Example 6

Homopropylene was prepared in the same manner as in Example 1, except that hydrogen was added in an amount of 3000 eggs. Comparative Example 7

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.

[Table 1]

Test Example 1

The properties of the polypropylene prepared in Examples and Comparative Examples were evaluated in the following manner.

(1) Melt Index (MI, g / 10 min): Measured at 230 ^° C under a load of 2.16 kg according to ASTM D1238 and expressed as the weight (g) of the polymer melted for 10 minutes.

(2) 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.

(3) Melting point (Tm, ^° C)

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.

(4) Polymer molecular weight distribution (MWD, polydispersity index): molecular weight distribution ("'Mw / Mn") was determined by measuring the Mw and Mn using gel permeation chromatography (GPC) and then determining the ratio of Mw / Mn. Specifically, it was measured using a Waters PL-GPC220 instrument using a Polymer Laboratories PLgel MIX-B 300 mm length column. At this time, the evaluation temperature was 160 ° C, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was 1 mL / min. Samples were prepared at a concentration of 10 mg / 10 mL and then fed in an amount of 200 yL. 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.

(5) Measurement of residual stress ratio

A sample was taken for the homopolypropylene according to the above Examples and Comparative Examples, and 200% strain was applied at 235 ^° C, and the change of the residual stress was measured for 10 minutes.

For the instantaneous residual stresses, a Discovery Hybrid Rheometer (DHR) from TA Instruments was used. The specimen was fully loaded between upper and lower plates with a diameter of 25 mm and melted ^at 235 ^° C. Respectively.

Based on the measured residual stress data, the ratio (RS%) of the residual stress according to the following formula (1) is calculated and shown in Table 2 below:

[Equation 1]

Residual stress ratio (Y) = (RSi / RS _{0) * 100}

In Equation 1, RSo is a residual stress at 200% strain on the sample fall 0.02 seconds (t _Q) was under 235 ^° C, R¾ is 1.00 seconds was added to the 200% strain on the sample under 235 ^° C () Is the residual stress.

[Table 2]

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As a result of the tests, the homopolypropylene of Examples 1 to 5 produced by the production method according to the present invention exhibited a narrow range of < RTI ID = 0.0 >

Low xylene soluble fraction and residual stress ratio,

And increased with increasing hydrogen input. 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.

In the case of Comparative Examples 2 to 4 in which compounds having different structures as the catalytically active material were used, the amount of hydrogen input required to produce polymers having equivalent levels was different due to the difference in hydrogen reactivity due to differences in catalyst structures, The molecular weight distribution was increased and the residual stress ratio was greatly increased as compared with Example 1 having a bump. In addition, the ligand structure is the same, but in the case of Comparative Example 7 using a compound containing a tether group of an alkoxyalkyl as a bridging group connecting two ligands, a high _ and a residual stress ratio were exhibited. From this, degradation of workability can be confirmed.

If the hydrogen supply amount condition is not satisfied even when the same catalyst is used, the melt index is excessively low or high as in Comparative Examples 5 and 6, and the degradation of workability can be confirmed. Test Example 2 <Nonwoven Fabrication>

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.

Specifically, homopolypropylene according to Examples and Comparative Examples was extruded using a 25 mm twin-screw extruder, 2000 ppm of Irganox 1010 ™ as an antioxidant,

A master batch containing 2000 ppm of Irgafos 168 ™ 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, and the die

235 ° C, primary air temperature and pressure were 300 ° C and 60 kPa (8.7 psi), polymer processing rate was 5.44 kg / hr and collector / die distance was 15.2 cm. <Evaluation of physical properties of nonwoven fabric

The properties of each of the spunbond nonwoven fabrics prepared using the homopolypropylene according to the Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Table 3 below.

(1) Weight of nonwoven fabric (gsm)

The weight of the manufactured nonwoven fabric was measured, and the weight of the nonwoven fabric per unit area was measured.

(2) Processability of nonwoven fabric

The production of nonwoven fabric was checked for the occurrence of single yarns, and the processability of the nonwoven fabric was evaluated according to the following criteria.

<Evaluation Criteria> Good: When the single yarn occurrence rate of the fibers is 10% or less, that is, 24 hours when the fibers are produced,

Poor: If the yarn incidence rate exceeds 10%, that is, 24 hours when the fiber is produced, and the time during which the fiber can not be produced due to single yarn occurrence is more than 2.4 hours

(3) Strength of nonwoven fabric

According to ASTM D 5035: 2011 (2015) method of the American Society for Testing and Materials, the machine direction (MD) and transverse direction (CD, cross di rect) of the nonwoven fabric were measured by a 5 cm width cut- ion was measured (Strength, N / 5 cm)

(4) Roughness of nonwoven fabric

The roughness of the nonwoven fabric was measured by ten blind panel evaluations and evaluated according to the following criteria:

◎: When there is more than 7 people in the evaluation of roughness on the feeling of nonwoven fabric, it is judged to be excellent

O: It is judged to be good when 4 ~ 6 persons are evaluated as rough for the feeling of nonwoven fabric

A: When there are 2 or 3 persons who are roughly evaluated to feel the nonwoven fabric feel,

X: judged to be bad when the evaluation of roughness on the feeling of nonwoven fabric is 1 or less

[Table 3]

According to one embodiment of the present invention, the nonwoven fabric prepared using the homopolypropylene of Examples 1 to 5, in which the MI, MWD, xylene solubles and the residual stress ratio were all optimized, exhibited excellent workability as well as high strength and roughness . Furthermore, it can be seen from the high roughness characteristics of the homopolypropylene according to Examples 1 to 5 that it is possible to manufacture a cleaning nonwoven fabric which requires high roughness characteristics, even without first blending with additives.

On the other hand, in the case of 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. In particular, from the low roughness characteristics, it can be seen that 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. In the case of 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.

Also, in 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 > On the other hand, in 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.

In the case of Comparative Example 7 in which a compound containing a tether group of an alkoxyalkyl was used as a bridging group connecting two ligands, the homopolypropylene produced had high MWD and residual stress, Respectively. From these results, it can be confirmed that the transition metal compound having the structure of the formula (1) is preferable for realizing the homopolypropylene satisfying the physical properties according to the present invention.

Claims

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Claims:

Claim 11

Homopolypropylene satisfying the following conditions:

0 Melt index 1) Measured from 230 to 2.161 _¾ load according to 1238) 200 to 200½ / 101 ₁₁

) Molecular weight distribution 3.3 or less

[Claim 2]

The method according to claim 1,

Wherein the homopolypropylene has a molecular weight distribution of 2.5 to 3.3. [3]

The method according to claim 1,

The homopolypropylene has a residual stress ratio of 0.02 to 0.03%. [4]

The method according to claim 1,

Wherein the homopolypropylene is a homopolypropylene having a selfalloy soluble fraction of 0.6 to 0.7% by weight. [5]

The method according to claim 1,

Wherein the homopolypropylene has a melting point of 150 to 1551:. [Claim 6] 2019/103306 1 »(: 1 ^ 1 {2018/011638

Methods Preparation of the presence of a catalyst composition comprising a compound of formula (1), by introducing hydrogen to 700 to 250如抑₁ including the step of polymerizing a propylene monomer, paragraph (1) homopolypropylene:

[Chemical Formula 1]

In Formula 1,

- Show is carbon, silicon or germanium,

XI and ₂ are each independently halogen,

Each of ¾ and ¾ is independently 0 _6-20 aryl substituted with 0 _1-20 alkyl, each of ¾ to ¾ and ¾ to ¾ is independently hydrogen, halogen, 0 _1-20 alkyl,

0 _2-20 alkenyl, 0 _1-20 alkylsilyl, 0 _1-20 alkyl, 0 _1-20 alkoxysilyl, ( ₂₀ ether, 0 _1-20 silylether, 0 _1-20 alkoxy, 0 _6-20 aryl , 0 _7-20 alkylaryl, or 0 _7-20 arylalkyl,

¾ and ¾ ° are the same as in the formula, and are _-20 alkyl.

[7]

The method according to claim 6,

Wherein the urine is silicon. 2019/103306 1 »(: 1 ^ 1 {2018/011638

8.

The method according to claim 6,

Wherein each of the above-mentioned ¾ and ¾ is independently a phenyl group substituted with 0 _3-6 branched alkyl groups.

5

9]

7. The method of claim _6,

Gt;

10

Claim 10

The method according to claim 6,

₁₅ [Claim 11]

The method according to claim 6,

Wherein the compound of formula (1) is a compound represented by the following formula.

[Formula _3]

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Claim 12

The method according to claim 6,

Wherein the compound of Formula 1 is supported on a carrier.

Claim 13

The method according to claim 6,

Wherein the catalyst composition further comprises at least one of a compound represented by the following formula (2), a compound represented by the following formula (3), and a compound represented by the following formula (4)

(2)

- [(¾ ₁ ) -0] "

In Formula 2, 2019/103306 1 »(: 1 ^ 1 {2018/011638

A hydrocarbon having up to ₂₀ hydrocarbons substituted with halogen;

Mee is an integer of 2 or more;

(3)

1 (¾ 2) 3

. In Formula 3,

One? ₁₂ are the same or different from each other, and each independently halogen; ( ₂₀ hydrocarbons; or substituted with halogen ( ₂₀ hydrocarbons;

1 is aluminum or boron;

[Chemical Formula 4]

My] ⁺ [2¾] - or Re + [2¾

In Formula 4,

The table is a neutral or cationic Lewis base;

II is a hydrogen atom;

a group 13 element;

Each of which is the same or different from each other, is independently an aryl group of 0 ₅ to ₂₀ or an alkyl group of _-20 , wherein at least one hydrogen atom is substituted with halogen, a hydrocarbon, alkoxy or phenoxy or unsubstituted. (Ii)

A cleaning nonwoven fabric comprising homopolypropylene according to claim 1.