KR20100032556A - Olefin polymer resin composition for pipe and pipe produced by thereof - Google Patents

Abstract

The present invention relates to an olefinic polymer resin composition for pipes and pipes produced therefrom. The olefin-based polymer resin composition for pipes according to the present invention uses an olefin-based polymer having a molecular weight distribution and a melt flow rate ratio (MFRR) value in a range suitable for processing, and a selected processing aid as an optimum composition. When processing, the extrusion load is small, the extrusion amount is large, and the die-deposit (Die-Deposit) generation and the generation of fumes (fume) has a low productivity has excellent advantages. In addition, the pipe produced therefrom is excellent in appearance characteristics such as glossiness, whiteness and the like.

Description

Olefin-based polymer resin composition for pipes and pipes produced therefrom {OLEFIN POLYMER RESIN COMPOSITION FOR PIPE AND PIPE PRODUCED BY THEREOF}

The present invention relates to an olefinic polymer resin composition for pipes and pipes produced therefrom. The olefin-based polymer resin composition for pipes according to the present invention uses an olefin-based polymer having a molecular weight distribution and a melt flow rate ratio (MFRR) value in a range suitable for processing, and a selected processing aid as an optimal composition.

A number of methods for producing polyethylene resins having good processability and mechanical properties and excellent appearance have been proposed, but blends and techniques generally used up to now have various disadvantages.

Low density polyethylene (LDPE) and polyethylene vinyl acetate (EVA) copolymers are used to make high gloss articles with very smooth surface finishes, but they lack rigidity and require thick walls when used in pressurized fluids. Polyethylene materials that provide very high stiffness are characterized by very rough surfaces by surface crystallization of polymers. Thus, articles produced using such polymers have a matte finish.

Coextrusion of high density polyethylene (HDPE) with an outer thin layer of polyamide has been used to yield very high gloss products, but this method requires an adhesive layer between the high density polyethylene (HDPE) and the polyamide layer. Has a big disadvantage.

In addition, a method of blending low density polyethylene (LDPE) in order to improve the processability of polyethylene has been proposed, but it is not preferable due to the kneading problem of the product and the increase in processing cost.

Because of these disadvantages of polyethylene resins, it is most preferable to use a single resin rather than a composite use of resins, and to realize excellent pipe formability and appearance by introducing a polymer restructuring and an appropriate polymer processing aid. However, in general, polyethylene products made of Ziegler-Natta and metallocene catalysts have a narrow molecular weight distribution and show many problems in their use alone.

US Pat. No. 6,180,736 describes a process for producing polyethylene in a single gas phase reactor or a continuous slurry reactor using one metallocene catalyst. When using this method, polyethylene production cost is low, fouling hardly occurs, and polymerization activity is stable. In addition, US Pat. No. 6,911,508 describes the preparation of polyethylenes with improved metallurgical properties using a new metallocene catalyst compound and polymerized in a single gas phase reactor using 1-hexene as a comonomer. However, the polyethylene produced in the above patents also has a disadvantage in that it has a narrow molecular weight distribution, and thus it is difficult to exhibit sufficient impact strength and workability.

US Pat. No. 4,935,474 describes a process for producing polyethylene having a broad molecular weight distribution using two or more metallocene compounds. In addition, US Pat. No. 6,841,631 and US Pat. No. 6,894,128 produce polyethylene having bimodal or multimodal molecular weight distribution using a metallocene catalyst using at least two metal compounds, wherein the polyethylene is a film, pipe, It is described that it is applicable to the manufacture of blow molded articles. However, the polyethylene thus produced has an improved processability, but the dispersion state by molecular weight in the unit particles is not uniform, so that even in relatively good processing conditions, the appearance is rough and the physical properties are not stable.

Against this backdrop, there is a constant demand for the manufacture of pipe use resins having excellent mechanical strength and better processability.

The present invention uses an olefin-based polymer having a molecular weight distribution and a melt flow rate ratio (MFRR) value in a range suitable for processing, and a selected processing aid as an optimal composition. It is an object of the present invention to provide an olefinic polymer resin composition for pipes having excellent productivity due to less die-deposit generation and less fume generation and a pipe having excellent appearance characteristics produced therefrom.

The present invention

1) an olefin polymer, and

2) Fluoro-based processing aids containing fluoroelastomer

It provides an olefin-based polymer resin composition for pipes comprising a.

In addition, the present invention provides a method for producing a pipe having a processing temperature of 170 ° C. or more during the processing step by the extruder, using the pipe olefin polymer resin composition.

In addition, the present invention provides a pipe produced by the manufacturing method.

The olefin-based polymer resin composition for pipes according to the present invention is an olefin polymer having a molecular weight distribution and a melt flow rate ratio (MFRR) value in a range suitable for processing, and using a selected processing aid as an optimal composition In the process, the extrusion load is low, the extrusion amount is large, and the die-deposit and the generation of fume (fume) has a low productivity has excellent advantages. In addition, the pipe produced therefrom is excellent in appearance characteristics such as glossiness and whiteness.

Hereinafter, the present invention will be described in detail.

The olefinic polymer resin composition for pipes according to the present invention comprises a fluorine-based processing aid comprising 1) an olefinic polymer and 2) a fluoroelastomer.

In the olefin polymer resin composition for pipes according to the present invention, the 1) olefin polymer may be prepared using a hybrid supported metallocene catalyst having at least two different metallocene compounds supported on one carrier. have.

In the hybrid supported metallocene catalyst, the first metallocene compound, which is one of at least two different metallocene compounds, is a compound represented by the following Chemical Formula 1, and the second one is another one of the metallocene compounds. It is preferable to use the hybrid supported metallocene catalyst which is a compound represented by following formula (2) as a metallocene compound.

(L ¹ ) _p (L ² ) MQ _{3 -p}

In Chemical Formula 1,

M is a periodic table Group 4 transition metal,

L ¹ and L ² are each independently a radical of hydrogen, C _{1 ~ 20} 14 is substituted by an alkyl radical, a hydrocarbyl radical of a C _{2 ~ 20} alkenyl radicals, C _{6 ~ 30} aryl radicals, C _{7 ~ 30} alkylaryl radical, C _{7 ~ 30} arylalkyl radicals, C _{1 ~ 20} of the A metalloid radical of a group metal, or a ligand in which two neighboring carbon atoms are connected by a hydrocarbyl radical to form a 4-8 octacyclic ring,

Q is a halogen radical, C _{1 ~ 20} Alkyl radical, a C _{2 ~ 20} alkenyl radicals, C _{6 ~ 30} aryl radicals, C _{7 ~ 30} alkylaryl radical, or arylalkyl radical in C _{7 ~ 30,} and the two Q is C _{1 ~ 20} with the in Can form hydrocarbon rings,

p is 1 or 0,

In Chemical Formula 2,

M is a periodic table Group 4 transition metal;

R ¹ is the same or different and each independently represents an aryl radical of C _{1 ~ 20} alkyl radicals, C _{2 ~ 20} alkenyl radicals, C _{3 ~ 30} cycloalkyl radicals, C _{6 ~ 30} of each other, C _{7 ~ 30} alkyl aryl radicals, C _{7 ~ 30} aryl-alkyl radical, or a C _{8 ~ 30} arylalkyl radical;

Q and Q 'are the same or different and are each independently a halogen radical, a C _{1 ~ 20} alkyl radical, an alkylaryl radical of C _{2 ~ 20} alkenyl radicals, C _{6 ~ 30} aryl radicals, C _{7 ~ 30} of the , or aryl alkyl radical of C _{7 ~ 30} and, Q and Q 'may form a hydrocarbon ring of C _{1 ~ 20} taken together;

B is an alkylene radical of C _{1 ~ 4,} a dialkyl silicon, germanium, alkyl phosphine, or amine, with two cyclopentadienyl based ligands, or a cyclopentadienyl ligand and JR ² _z share series combination _-y A leg tied by;

R ² is a hydrogen radical, an aryl radical of C _{1 ~ 20} alkyl radicals, C _{2 ~ 20} alkenyl radicals, C _{6 ~ 30} aryl radicals, C _{7 ~ 30} alkylaryl radicals or C _{7 ~ 30} of the of the a ;

J is a periodic table group 15 element or group 16 element;

z is the oxidation number of the element J;

y is the bond number of the J element;

n and n 'are the same as or different from each other, and each independently represent a positive integer of 0 or more;

r is an integer from 0 to 3;

Y represents a hetero atom of O, S, N or P;

A represents hydrogen or an alkyl radical of _{1 to 10} carbon atoms.

In the presence of a hybrid supported metallocene catalyst having at least two different metallocene compounds supported on one carrier, an olefin polymer having a molecular weight distribution curve of two or more can be prepared.

As a carrier that can be used in the preparation of the hybrid supported metallocene catalyst, silica, silica-alumina, silica-magnesia, etc. dried at high temperature may be used, and these are usually Na ₂ O, K ₂ CO ₃ , BaSO ₄ , Mg (NO ₃₎ may comprise an oxide, carbonate, sulfate, nitrate component of _2, and so on.

The amount of hydroxyl groups (-OH) on the surface of the carrier is preferably as low as possible, but it is practically difficult to remove all hydroxyl groups (-OH). Therefore, the amount of hydroxyl group (—OH) is preferably 0.1 to 10 mmol / g, more preferably 0.1 to 1 mmol / g, most preferably 0.1 to 0.5 mmol / g. The amount of the surface hydroxyl group (-OH) can be controlled by the preparation conditions or methods of the carrier, or the drying conditions or methods (temperature, time, pressure, etc.). In addition, in order to reduce side reactions caused by some of the hydroxyl groups remaining after drying, a carrier chemically removed from the hydroxyl group (—OH) may be used while preserving the highly reactive siloxane group participating in the supported.

Among the mixed supported metallocene catalyst components, the first metallocene compound mainly acts to make a low molecular weight olefin polymer, and the second metallocene compound mainly acts to make a high molecular weight olefin polymer, and thus is a bimodal or polycrystalline Olefin-based polymers having a molecular weight distribution are possible.

The inherent olefin polymer obtained by the first metallocene compound has a low molecular weight in the range of 1,000 to 100,000, and the olefin polymer obtained by the second metallocene compound has a high molecular weight in the range of 10,000 to 1,000,000. It is preferable that the olefin polymer obtained by the second metallocene compound has a higher molecular weight than the olefin polymer obtainable by the first metallocene compound.

The hybrid supported metallocene catalyst

a) preparing an activated supported metallocene catalyst by contacting a supported metallocene catalyst carrying at least one metallocene compound with a cocatalyst; And

b) further supporting at least one metallocene compound different from the metallocene compound on the activated supported metallocene catalyst;

It may be prepared by a manufacturing method comprising a.

For example, one metallocene compound inducing a low molecular weight olefinic polymer and one metallocene compound inducing a high molecular weight olefinic polymer are impregnated with one carrier together with a cocatalyst in a single reactor. The hybrid supported metallocene catalyst which can easily adjust the molecular weight distribution can also be produced by the reaction of.

Representative cocatalysts that can be used to activate the metallocene compounds include alkyl aluminum-based trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum, methyl aluminoxane, ethyl aluminoxane and isobutyl aluminoxane. And butyl aluminoxane, and the like, but a neutral or ionic compound of the boron-based tripentafluorophenyl boron, tributyl ammonium tetrapentafluorophenyl boron and the like, but is not limited thereto.

The content of the Group 4 transition metal of the periodic table in the mixed supported metallocene catalyst finally prepared in the present invention is preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, and 1 to 3% by weight. Most preferred. When the content of the Group 4 transition metal of the periodic table exceeds 20% by weight, the catalyst may deviate from the carrier during polymerization of the olefin, causing problems such as fouling, and manufacturing costs are increased.

In addition, the molar ratio of the Group 13 metal / 4 group metals of the periodic table in the hybrid supported metallocene catalyst is preferably 1 to 10,000, more preferably 1 to 1,000, and most preferably 10 to 100.

In addition, the supporting amount of the second metallocene compound is preferably supported at various molar ratios of 0.5 to 2 based on the moles of the first metallocene compound to variously control the molecular weight distribution of the final polyolefin.

The amount of the promoter supported is preferably in the range of 1 to 10,000 moles based on 1 mole of the metal contained in the first and second metallocene compounds, based on the metal included in the promoter.

The hybrid supported metallocene catalyst may be used for olefin polymerization by itself, or may be used for prepolymerization by contact with an olefin monomer such as ethylene, propylene, 1-butene, 1-hexyne, 1-octene, and the like.

The mixed supported metallocene catalyst of the present invention includes aliphatic hydrocarbon solvents having 5 to 12 carbon atoms such as isobutane, pentane, hexane, heptane, nonane, decane and isomers thereof; Aromatic hydrocarbon solvents such as toluene and benzene; Dilution in slurry form in hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene can be injected. The solvent is preferably used by removing a small amount of water, air, etc., which act as a catalyst poison by treating a small amount of aluminum.

In the olefin polymer resin composition for pipes according to the present invention, the 1) olefin polymer is preferably a homopolymer of an olefin monomer or a copolymer of an olefin monomer and an alpha olefin comonomer.

Examples of the olefin monomers include ethylene, propylene, butene, pentene, hexene, octene, decene, dodecene, tetradecene, hexadecene, octadecene and eicosene, but are not limited thereto.

By using the hybrid supported metallocene catalyst, an olefin copolymer having a molecular weight distribution curve of two or more tablets may be prepared. In particular, copolymerization with alpha olefin comonomers when using a hybrid supported metallocene catalyst is induced by a second metallocene compound that forms a high molecular weight moiety so that the alpha olefin comonomer is concentrated at the high molecular weight chain side. Olefin copolymers can be prepared.

As the comonomer used in the copolymerization, an alpha olefin having 4 or more carbon atoms may be used. Alpha-olefins having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like, but is not limited thereto. Of these, alpha olefins having 4 to 10 carbon atoms are preferable, and one or several kinds of alpha olefins may be used together as a comonomer.

The ethylene content of the olefin copolymer is preferably 55 to 99% by weight, more preferably 65 to 98% by weight, most preferably 70 to 96% by weight. The structural unit derived from an alpha olefin having 4 or more carbon atoms is preferably 1 to 45% by weight, more preferably 2 to 35% by weight, most preferably 4 to 20% by weight.

The production of the olefin polymer may be carried out according to the conventional method by continuously supplying an alpha olefin having at least 4 carbon atoms as ethylene and comonomer at a constant rate using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor, or solution reactor. Can be.

The polymerization temperature when copolymerizing ethylene and a high alpha olefin having 4 or more carbon atoms as a comonomer using the hybrid supported metallocene catalyst of the present invention is preferably 25 to 500 ° C, more preferably 25 to 200 ° C, and 50 150 degreeC is more preferable. In addition, the polymerization pressure is preferably performed at 1 to 100 Kgf / cm ² , more preferably 1 to 50 Kgf / cm ² , and most preferably 5 to 30 Kgf / cm ² .

The olefin copolymer according to the present invention can be obtained by copolymerization of ethylene and an alpha olefin having 4 or more carbon atoms using the hybrid supported metallocene compound as a catalyst, and has a bimodal or polycrystalline molecular weight distribution.

It is well known that olefin polymers polymerized with a metallocene catalyst have superior remarkability in terms of physical properties because of the lower reactivity of catalyst residues than polyolefins polymerized with a Ziegler-Natta catalyst. However, there is a disadvantage in that the molecular weight is generally uniform, the molecular weight distribution is narrow, and the distribution of alpha olefin comonomers is also uniform, resulting in poor workability. In particular, in extrusion pipe molding, there is a problem that productivity is significantly reduced due to the extruded load, and the appearance of the product is not good, and thus it is difficult to apply the field. In other words, in order to use the polymer where high stress cracking resistance (FNCT) and high strength resin are required such as pipes, and it is essential to increase the molecular weight in order to improve such physical properties, the high molecular weight portion of the comonomer content is absolutely insufficient in terms of processability. There was a difficulty.

However, by using the hybrid supported metallocene catalyst of the present invention, it is possible to prepare an olefin polymer having a molecular weight distribution of 5 to 30, including a low molecular weight and a high molecular weight portion, and showing a bimodal or polycrystalline molecular weight distribution curve. The olefin-based polymers thus prepared not only have excellent processability when forming products, but also the alpha olefin comonomers are intensively copolymerized in the high molecular weight ethylene chain, so that tensile strength, impact strength, environmental stress cracking resistance (ESCR), and stress cracking FNCT has very good characteristics.

In the olefin polymer resin composition for pipes according to the present invention, the density of the 1) olefin polymer is affected by the amount of alpha olefin comonomer used. In other words, if the amount of the alpha olefin comonomer is large, the density is low, and if the amount of the alpha olefin comonomer is low, the density is high. The resin of the present invention has a density of from 0.920 to 0.960 g / cm ³ , particularly from 0.930 to 0.950 g / cm ³ , in order to obtain optimum physical properties of pipe products.

In addition, the melt flow index (190 ° C., 2.16 kg load condition) of the above 1) olefin polymer is 0.05 to 2 g / 10 minutes, particularly 0.1 to 1 g / 10 minutes, so that the molding processability and the mechanical properties can be harmonized. It is preferable as a point.

In addition, the MFRR value of the 1) olefin polymer is 38 to 150 is most preferable for the appearance, processability and physical properties of the pipe product.

In addition, the 1) olefin polymer is 0 to 9 SCB content per 1,000 carbons of the olefin polymer, it is preferable that the comonomer content is 0 to 5.5 wt%.

However, the processability improvement by the polymer structure is limited, and various kinds of processing aids are usually used.

The olefin-based polymer resin composition for pipes according to the present invention includes a fluorine-based processing aid, thereby further improving surface glossiness, further improving melt stability, and maintaining a suitable melt tension. The skin's skin can be removed.

In the olefin polymer resin composition for pipes according to the present invention, the 2) fluorine-based processing aid is characterized in that it comprises a fluoroelastomer (fluoroelastomer). The fluoroelastomer is also called teflon-elastomer copolymer.

The ethylene content of the fluoroelastomer is 35 to 55% by weight, and the content of fluorine is preferably 45 to 65% by weight, but is not limited thereto.

In the fluoroelastomer, it is preferable to include poly (vinylidene fluoride) (PVDF), poly (hexafluoropropylene) (PHFP) and poly (tetrafluoro ethylene) (PTFE). The molar ratio is preferably PVDF: PHFP: PTFE = (0.9 to 1.3): (0.8 to 1.2): (4 to 6), but is not limited thereto.

The fluoroelastomer may include a few ppm level of hardener.

More specific examples of the fluoroelastomer include Dynamar ^™ FX-9613, FX-5920A, FX5911X, etc. manufactured by 3M, but are not limited thereto.

In the olefin-based polymer resin composition for pipes according to the present invention, the content of the 2) fluorine-based processing aid is preferably from 100 to 5,000 ppm, preferably 300 to 2,000 ppm, based on the weight of the 1) olefin-based polymer resin. More preferably, but is not limited thereto.

The olefinic polymer resin composition for pipes according to the present invention may further include other additives. Specifically, such additives include heat stabilizers, antioxidants, UV absorbers, light stabilizers, metal inerts, fillers, reinforcing agents, plasticizers, lubricants, emulsifiers, pigments, optical bleaches, flame retardants, antistatic agents, foaming agents, and the like. The type of the additive is not particularly limited and may be a general additive known in the art.

In addition, the method for producing a pipe according to the present invention is characterized in that the processing temperature is 170 ° C. or more during the processing by the extruder using the olefin polymer resin composition for pipe. The processing temperature is more preferably 170 ℃ to 260 ℃.

In the production of the pipe according to the present invention, when the olefinic polymer resin composition is subjected to shearing in the melt state in the extruder, the fluorine-based processing aid is characterized by low molecular weight and low melting point, which are characteristics of the elastomer unit. It effectively moves in the direction of the extruder barrel. Subsequently, the fluorine (F) of the fluorine-based processing agent forms a strong hydrogen bond with the iron oxide on the surface of the extruder barrel made of iron, and is not easily discharged out of the extruder, and stays for a long time while being coated on the extruder barrel. In addition, since a very small amount of a hardening agent of several ppm is added to the fluorine-based processing aid, the die and the barrel are strongly coated while being gradually crosslinked when subjected to heat for a long time on the surface of the extruder barrel. That is, as the die is smoothly coated, the gloss of the appearance of the molding is rapidly improved.

Therefore, in the manufacture of the pipes according to the invention, it is preferable to pre-running the extruder for at least one hour in order to exert the performance of the fluorine-based processing aid. That is, in the initial stage of extrusion, the appearance of the molding may be somewhat worse than that of not adding the fluorine-based processing aid, but after about one hour, the appearance of the molding becomes very excellent.

In the manufacture of the pipe according to the present invention, since crosslinking by the fluorine-based processing aid occurs at 170 ° C or higher, processing at 170 ° C or higher is appropriate, and processing at 170 ° C to 260 ° C is more preferable. In the case of processing at a temperature lower than the ℃ may exhibit a deterioration of the appearance of the molding.

¹⁹ F-NMR analysis and differential scanning calorimetry (DSC) results of Dynamar ^TM FX-9613 manufactured by 3M, a fluorine processing aid applied in Example 1, described below, are shown in FIGS. 1 and 2, respectively.

In FIG. 2, the endothermic peak occurring at 60 ° C. is the melting point (Tm) peak by the elastomer part in the fluoroelastomer, where the fluoroelastomer moves toward the wall of the die and barrel during extrusion. It will play a big role. In addition, from a broad exothermic peak occurring at 176 ° C. or more, the Teflon die coating effect may be exhibited by crosslinking with a few ppm level of curing agent contained in the resin.

The present invention also provides a pipe manufactured according to the method for producing the pipe.

The pipe according to the present invention is excellent in appearance characteristics such as glossiness, whiteness.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, an Example is for illustrating this invention and this invention is not limited only to these.

< Example >

The organic reagents and solvents required for catalyst preparation and polymerization were purified by Aldrich's standard method, and ethylene was used by high-purity products from Applied Gas Technology through water and oxygen filtration devices. It was. The reproducibility of the experiment was enhanced by blocking contact between air and moisture at all stages of catalyst synthesis, loading and olefin polymerization.

To verify the structure of the catalyst, spectra were obtained using 300 MHz NMR (Bruker). Apparent density was measured by a method specified in DIN 53466 and ISO R 60 using an apparent tester (Apparent Density Tester 1132, manufactured by APT Institute fr Prftechnik).

< Production Example  1> first Metallocene  Preparation of the catalyst-[ ^t Bu -O- ( CH ₂ ) ₆ - C ₅ H ₄ ] ₂ ZrCl ₂ Synthesis of

Using 6-chlorohexanol, t-Butyl-O- (CH ₂ ) ₆ -Cl was prepared by the method shown in Tetrahedron Lett. 2951 (1988), and reacted with NaCp. t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ was obtained (yield 60%, bp 80 ° C./0.1 mmHg). Further, t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78 ° C, and normal butyllithium (n-BuLi) was slowly added, and the temperature was raised to room temperature. I was. The solution was again slowly added a lithium salt solution synthesized to a suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol) / THF (30 mL) at -78 ° C. The reaction was further reacted at room temperature for 6 hours. All volatiles were dried in vacuo and the resulting oily liquid material was filtered off by addition of hexane solvent. The filtered solution was dried in vacuo and hexane was added to induce precipitate at low temperature (-20 ° C). The obtained precipitate was filtered at low temperature to give [ ^t Bu-O- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl _{2 as a} white solid. The compound was obtained (yield 92%).

¹ H NMR (300 MHz, CDCl ₃ ): 6.28 (t, J = 2.6 Hz, 2H), 6.19 (t, J = 2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.62 ( t, J = 8 Hz), 1.7-1.3 (m, 8 H), 1.17 (s, 9 H).

¹³ C NMR (CDCl ₃ ): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00.

< Production Example  2> second Metallocene  Preparation of the catalyst-[ methyl (6-t- buthoxyhexyl ) silyl (η ⁵ -tetramethylCp) (t-Butylamido)] TiCl ₂ Synthesis of

50 g of Mg (s) was added to a 10 L reactor at room temperature, followed by 300 mL of THF. After adding 0.5 g of I ₂ , the reactor temperature was maintained at 50 ° C. After the reactor temperature was stabilized, 250 g of 6-t-butthoxyhexyl chloride was added to the reactor at a rate of 5 mL / min using a feeding pump. As the 6-t-butoxyhexyl chloride was added, it was observed that the reactor temperature increased by about 4 to 5 ° C. The mixture was stirred for 12 hours while adding 6-t-butoxyhexyl chloride. After 12 hours of reaction, a black reaction solution was obtained. After taking 2 mL of the resulting black solution, water was added to obtain an organic layer, and 6-t-butoxyhexane was confirmed by ¹ H-NMR, and 6-t-butoxyhexane was extracted. It was found that the nyad reaction proceeded well. Thus, 6-t-butoxyhexyl magnesium chloride was synthesized.

500 g of MeSiCl ₃ and 1 L of THF were added to the reactor, and the reactor temperature was cooled to -20 ° C. 560 g of the synthesized 6-t-butoxyhexyl magnesium chloride was added to the reactor at a rate of 5 mL / min using an infusion pump. After completion of the Grignard reagent injection, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours, it was confirmed that a white MgCl ₂ salt was produced. 4 L of hexane was added to remove the salt through a laboratory pressure dewatering filtration apparatus (labdori, Han River Engineering Co., Ltd.) to obtain a filter solution. The resultant filter solution was added to the reactor, and hexane was removed at 70 ° C. to obtain a pale yellow liquid. The obtained liquid was confirmed to be the desired methyl (6-t-butoxyhexyl) dichlorosilane compound through ¹ H-NMR.

¹ H-NMR (CDCl ₃ ): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 (s, 3H) .

1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to the reactor, and the reactor temperature was cooled to -20 ° C. 480 mL of n-BuLi was added to the reactor at a rate of 5 mL / min using an infusion pump. After n-BuLi was added, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours of reaction, an equivalent of methyl (6-t-butoxy hexyl) dichlorosilane (Methyl (6-t-buthoxy hexyl) dichlorosilane, 326 g, 350 mL) was added quickly to the reactor. After stirring for 12 hours while slowly raising the reactor temperature to room temperature, the reactor temperature was further cooled to 0 ° C., and then 2 equivalents of t-BuNH ₂ was added thereto. Stirring for 12 hours while slowly raising the reactor temperature to room temperature. After 12 hours of reaction, THF was removed and 4 L of hexane was added to obtain a filter solution from which salt was removed through labdori. After the filter solution was added to the reactor again, hexane was removed at 70 ° C. to obtain a yellow solution. The resulting yellow solution was identified as methyl (6-t-butoxyhexyl) (tetramethylCpH) t-butylaminosilane (Methyl (6-t-buthoxyhexyl) (tetramethylCpH) t-Butylaminosilane) compound by ¹ H-NMR. Could. TiCl ₃ (THF) ₃ (10 mmol) to a dilithium salt of a ligand of -78 ° C synthesized in THF solution from n-BuLi and ligand dimethyl (tetramethylCpH) t-butylaminosilane (Dimethyl (tetramethylCpH) t-Butylaminosilane) Was added quickly. The reaction solution was slowly stirred at -78 ° C to room temperature for 12 hours. After stirring for 12 hours, an equivalent amount of PbCl ₂ (10 mmol) was added to the reaction solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, a dark black solution was obtained. After THF was removed from the reaction solution, hexane was added to filter the product. Remove hexane from the filter solution obtained, and then remove the desired [methyl (6-t-buthoxyhexyl) silyl (η ⁵ -tetramethylCp) (t-Butylamido)] TiCl ₂ from ¹ H-NMR. It was confirmed that the compound.

¹ H-NMR (CDCl ₃ ): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 to 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H) , 0.7 (s, 3H)

< Production Example  3> Hybrid Support Metallocene  Preparation of the catalyst

Silica (XPO 2412, manufactured by Grace Davison) was dehydrated under vacuum at 800 ° C. for 15 hours. 1.0 g of this silica was added to three glass reactors, 10 mL of hexane was added thereto, and 10 mL of a hexane solution in which the "first metallocene" compound selected in Preparation Example 1 was dissolved was added thereto, followed by stirring at 90 ° C for 4 hours. Let. After the reaction was completed, the stirring was stopped, and the hexane was separated by layer, and then washed three times with 20 mL of hexane solution. A methylaluminoxane (MAO) solution containing 12 mmol aluminum was added to the toluene solution, and the reaction was slowly stirred at 40 ° C. Thereafter, the toluene was washed with a sufficient amount of toluene to remove the unreacted aluminum compound, and the remaining toluene was removed under reduced pressure at 50 ° C. The solid thus prepared may be used as a catalyst for olefin polymerization without further treatment. To prepare a hybrid catalyst, a toluene solution in which the "second metallocene" compound prepared in Preparation Example 2 was dissolved in the supported catalyst obtained above was added to a glass reactor and stirred at 40 ° C for reaction. Thereafter, the mixture was washed with a sufficient amount of toluene and then vacuum dried to obtain a solid powder. The final catalyst thus prepared may be used directly for polymerization, or may be used for prepolymerization which is carried out at room temperature for 1 hour by adding 30 psig ethylene for 2 minutes.

<Preparation and Characterization of Olefin Copolymer>

Using the hybrid supported metallocene catalyst prepared above, an olefin copolymer was prepared according to the conventional method in the polymerization reactor according to the respective conditions in Examples 1 to 6 and Comparative Examples 1 to 4 below. Evaluation items and evaluation methods of the olefin copolymer obtained here are as follows. Pipe physical properties were evaluated by molding pipes to the outside diameter of 32mm, thickness of 2.9mm.

(Raw material property)

1) Density: Measured based on ASTM D1505.

2) Melt index (MI, 2.16kg): Measured based on the measurement temperature 190 ℃, ASTM 1238.

3) MFRR (MFR ₂₀ / MFR ₂ ): MFR ₂₀ Melt index (MI, 21.6 kg load) divided by MFR ₂ (MI, 2.16 kg load).

4) Molecular weight, molecular weight distribution: The number average molecular weight, the weight average molecular weight, and the Z average molecular weight were measured using a measurement temperature = 160 ° C., gel permeation chromatography-FTIAL (GPC-FTIR). The molecular weight distribution was calculated by the ratio of the weight average molecular weight and the number average molecular weight.

(Product appearance)

1) Glossiness: 60 degree reflection glossiness was measured using a gloss meter.

2) YI (Yellow Index): . To put the pellet (pellet) cell (cell) in a state using a colorimeter ^{(HunterLab ColorQUEST ® HUNTER ASSOCIATES LABORATORY,} INC, USA) was measured repeated three times.

3) Pipe appearance: visual observation, judged as good / normal / bad.

(Pipe workability)

1) Resin pressure (bar): The resin melt pressure generated at the extrusion site during pipe processing under the pipe product processing conditions was measured. Resin temperature was 200 degreeC, mold temperature was 20 degreeC, and resin extrusion rate was 50 kg / hr.

2) Ship speed: Workability (m / min) is evaluated by measuring the work speed (m / min) when forming pipes

3) Die-Deposit: A low molecular weight material formed at the edge of die surface during pipe forming. Pipe forming for 3 hours, visual observation.

a) Time of occurrence: The time when the die-deposit was first formed (<3hr)

b) Generation: Visual observation, determined by 多 / 中 / 小 / 無.

4) Fume occurrence: Visual observation, judged by 多 / 中 / 小 / 無.

(Mechanical properties)

1) Pressure resistance characteristics: The time to apply the test stress under the condition of 3.6Mpa in hot water at 95 ℃ and to break it. Measured up to 800 hours.

2) Stress crack resistance (FNCT): The stress crack resistance test method of the molding composition of the present invention is described in M. Flissner in Kunststoffe 77 (1987), pp. 45 et seq.], Which corresponds to ISO / FDIS 16770, which is in effect today. In ethylene glycol, a stress crack facilitating medium using a tension of 6.0 Mpa at 80 ° C., the break time was shortened due to the shortening of the stress initiation time by the notch (1.6 mm / safety razor blade). Specimens were fabricated by sawing three specimens of dimensions 10 mm wide, 10 mm long and 90 mm long from a compressed nameplate of thickness 10 mm. The notch element specifically manufactured for this purpose uses a safety razor blade to provide the central notch to the specimen. Notch depth is 1.6 mm. Measured up to 7,000 hours.

< Comparative example  1>

The mixed supported metallocene catalyst (1) obtained in Preparation Example 3 was introduced into a single loop slurry polymerization process to prepare polyethylene for pipe use according to the conventional method. 1-hexene was used as comonomer. The obtained polyethylene copolymer was granulated at an extrusion temperature of 160 to 200 ° C. using a twin screw extruder (W & P Twin Screw Extruder, 44 pie, L / D = 30) after formulating an appropriate amount of antioxidant (3,000 to 7,000 ppm). Pipe molding was extruded using a single screw extruder (Battenfeld Pipe M / C, 50 pie, L / D = 22, compression ratio = 3.5) to the specification of the outer diameter 32mm, thickness 2.9mm at 170 ~ 210 ℃ extrusion temperature. Raw material properties, product appearance, pipe workability and mechanical properties of the polyethylene copolymer were carried out according to the property evaluation method of Examples, and the results are shown in Tables 2 to 4.

< Example  1>

Extruded granulated polyethylene copolymer, except that 300ppm fluorine processing aid (Dynamar ^TM FX-9613, manufactured by 3M) was obtained by the same method and conditions as in Comparative Example 1 to obtain a pipe molding, the characteristics evaluation results 2 to 4 are shown.

< Example  2>

Extrusion granulation of the polyethylene copolymer, except that the fluorine-based processing aid (Dynamar ^TM FX-9613 manufactured by 3M) of 700ppm was obtained in the pipe molding was obtained in the same manner and conditions as in Comparative Example 1, the characteristics evaluation results 2 to 4 are shown.

< Example  3>

Extrusion granulation of polyethylene copolymer, except that 1,500ppm fluorine-based processing aid (Dynamar ^TM FX-9613, manufactured by 3M) was obtained in the same manner as in Comparative Example 1 to obtain a pipe molding, the characteristics evaluation results Tables 2-4 are shown.

< Example  4>

Extrusion granulation of polyethylene copolymers, except that preformed 2,000ppm fluorine processing aid (Dynamar ^TM FX-9613, manufactured by 3M) pipe moldings were obtained in the same manner and conditions as in Comparative Example 1, the characteristics evaluation results Tables 2-4 are shown.

< Comparative example  2>

Extrusion granulation of polyethylene copolymer, pipes were prepared in the same manner and in the same manner as in Comparative Example 1 except that 1,000 ppm of Mg-St processing aid (C ₃₆ H ₇₀ O ₆ Mg, Dubon Polylub-120) was prescribed. Molded products were obtained and characteristics evaluation results are shown in Tables 2-4.

< Comparative example  3>

Extrusion granulation of the polyethylene copolymer, Zn-St processing aid (Zn (C ₁₇ H ₃₅ COO) ₂ ), Songwon Industrial Co., Ltd. SONGSTAB SZ-210) Except that 1,000ppm was the same as in Comparative Example 1 Pipe moldings were obtained by the methods and conditions, and the results of the evaluation of the properties are shown in Tables 2 to 4.

< Comparative example  4>

A Ziegler-Natta catalyst was added to a single solution polymerization process to prepare a polyethylene copolymer according to the conventional method. 1-octene was used as comonomer. In the granulation and pipe molding of the obtained polyethylene copolymer, the polyethylene copolymer was prepared in the same manner as in Comparative Example 1 except that 300 ppm of a fluorine processing aid (Dynamar ^TM FX-9613, manufactured by 3M) was prescribed. , Characteristics evaluation results are shown in Table 2-4.

< Comparative example  5>

The metallocene catalyst was added to a single solution polymerization process to prepare a polyethylene copolymer according to the conventional method. 1-octene was used as comonomer. In the granulation and extrusion blow molding of the polyethylene copolymer obtained here, Zn-St processing aid (Zn (C ₁₇ H ₃₅ COO) ₂ ) at the time of extrusion granulation of the polyethylene copolymer, Songwon Industrial Co., Ltd. SONGSTAB SZ-210 ) Except for prescribing 1,000ppm was the same as in Comparative Example 1, the characteristics evaluation results are shown in Tables 2-4.

< Comparative example  6>

When the polyethylene copolymer was extruded and granulated, a pipe molding was obtained by the same method and conditions as in Comparative Example 1 except that 10,000 ppm of fluorine-based processing aid (Dynamar ^TM FX-9613, manufactured by 3M) was obtained. Tables 2-4 are shown.

In Examples 1 to 4, the ethylene content in the fluorine processing aid was 45% by weight, and the content of fluorine was 55% by weight as analyzed by IC (ion chromatography). In addition, as a result of ¹⁹ F-NMR analysis, the molar ratio of each type of Teflon in the fluorine-based processing aid was PVDF: PHFP: PTFE = 1.1: 1.0: 5.2.

As can be seen from Tables 1 to 4, the polyethylene copolymers obtained in Examples 1 to 4 are made of the same base resin having a bimodal and broad molecular weight distribution using a hybrid supported metallocene catalyst. Fluoro-based processing aid was used to adjust the content. As the content of the fluorine processing aid increased, the gloss and whiteness increased and the appearance was excellent. In addition, as the content of the fluoro-based processing aid increases, the resin pressure decreases, the line speed increases, and the problems of die-deposit and fume generation are remarkably improved.

In addition, as shown in Comparative Example 6, when the fluoro-based processing aids are prescribed in extremely large amounts, the appearance of the product is rather deteriorated, and the side-effect of a rapid increase in the amount of die-deposit and fume is caused. Could know. Thus, the optimum prescription range of the fluorine-based processing aid is 300 to 2,000 ppm. In this range, a pipe product having excellent gloss, whiteness, and pipe appearance, low resin pressure, and high productivity (speed) can be obtained. Could. In addition, the die-deposit generation is extremely limited within the optimum range of the fluorine-based processing aid, and the generation of fumes is reduced.

In Comparative Example 2, the base resin was the same as in Example, but the product was prescribed 1,000 ppm of Mg-St-based processing aid, and the improvement of product appearance and processability was inferior to that of the product prescribed the fluorine-based processing aid. It was.

In Comparative Example 3, the base resin was the same as in Example, but the product was prescribed 1,000 ppm of Zn-St-based processing aid, compared to the product prescribed the fluorine-based processing aid and the Mg-St-based processing aid. And poor processability, die-deposit and fume generation were serious.

Comparative Example 4 uses polyethylene polymerized using 1-octene as a comonomer in a single solution polymerization process using a Ziegler-Natta catalyst as a base resin, and has a typical narrow molecular weight distribution. For this reason, although 300 ppm of fluorine processing aid was prescribed, workability was very inferior. In addition, the molecular weight distribution was narrow and the comonomer distribution was inferior, resulting in poor pressure resistance and stress crack resistance (FNCT).

Comparative Example 5 uses polyethylene polymerized using 1-octene as a comonomer in a single solution polymerization process using a metallocene catalyst as a base resin, and has an extremely narrow molecular weight distribution. In addition, the Zn-St-based processing aid is prescribed, and despite the high Melt Index, it is inferior to Examples 2 to 4 in terms of gloss and workability. In addition, the molecular weight distribution was extremely narrow and the density was high, and the stress notch creep test (FNCT) was inferior.

Particularly, the results of observing the appearance of the pipe processed by adding 700 ppm of fluorine processing aid as in Example 2 of the present invention are shown in FIG. 1, and the pipe processed without adding a fluorine processing aid as in Comparative Example 1 The results of observing the appearance of SEM in FIG. 2 are shown. 1 and 2, it can be seen that the appearance of the pipe processed by adding the fluorine-based processing aid according to the present invention shows excellent surface smoothness compared to the appearance of the pipe processed without the fluorine-based processing aid.

Figure 1 is a ¹⁹ F-NMR analysis of the fluorine-based processing aids applied in Examples 1 to 4 of the present application.

Figure 2 is a diagram showing the differential scanning calorimetry (DSC) results of the fluorine-based processing aids applied in Examples 1 to 4 of the present application.

Figure 3 is a view of the appearance of the pipe of Example 2 of the present application observed by SEM.

4 is a diagram illustrating an appearance of a pipe of Comparative Example 1 of the present application with SEM.

Claims (13)

1) an olefin polymer, and 2) Fluoro-based processing aids containing fluoroelastomer Olefin polymer resin composition for pipe comprising a. The olefin-based polymer resin composition for pipes according to claim 1, wherein the ethylene content in the fluoroelastomer is 35 to 55% by weight, and the content of fluorine is 45 to 65% by weight. The method of claim 1, wherein the fluoroelastomer comprises poly (vinylidene fluoride) (PVDF), poly (hexafluoropropylene) (PHFP) and poly (tetrafluoro ethylene) (PTFE), These molar ratios are PVDF: PHFP: PTFE = (0.9-1.3) :( 0.8-1.2) :( 4-6), The olefin type polymer resin composition for pipes characterized by the above-mentioned. The olefin-based polymer resin composition for pipes according to claim 1, wherein the fluoroelastomer comprises at least one selected from the group consisting of 3M's Dynamar ^™ FX-9613, FX-5920A, and FX5911X. The olefin-based polymer resin composition for pipes according to claim 1, wherein the content of the fluorine-based processing aid is 100 to 5,000 ppm based on the weight of the olefin-based polymer resin. The method according to claim 1, wherein 1) the olefin polymer is prepared by using a hybrid supported metallocene catalyst having at least two different metallocene compounds supported on one carrier, the at least two different metals The first metallocene compound, which is one of the sen compounds, is a compound represented by the following Chemical Formula 1, and the second metallocene compound, which is the other one of the metallocene compounds, is a compound represented by the following Chemical Formula 2 Olefin-based polymer resin composition for: [Formula 1] (L ¹ ) _p (L ² ) MQ _{3 -p} In Chemical Formula 1, M is a periodic table Group 4 transition metal, L ¹ and L ² are each independently a radical of hydrogen, C _{1 ~ 20} 14 is substituted by an alkyl radical, a hydrocarbyl radical of a C _{2 ~ 20} alkenyl radicals, C _{6 ~ 30} aryl radicals, C _{7 ~ 30} alkylaryl radical, C _{7 ~ 30} arylalkyl radicals, C _{1 ~ 20} of the A metalloid radical of a group metal, or a neighboring two carbon atom, is a ligand which is connected by a hydrocarbyl radical to form a 4 to 8 angular ring, Q is a halogen radical, C _{1 ~ 20} Alkyl radical, a C _{2 ~ 20} alkenyl radicals, C _{6 ~ 30} aryl radicals, C _{7 ~ 30} alkylaryl radical, or arylalkyl radical in C _{7 ~ 30,} and the two Q is C _{1 ~ 20} with the in Can form hydrocarbon rings, p is 1 or 0, [Formula 2]

In Chemical Formula 2, M is a periodic table Group 4 transition metal; R ¹ is the same or different and each independently represents an aryl radical of C _{1 ~ 20} alkyl radicals, C _{2 ~ 20} alkenyl radicals, C _{3 ~ 30} cycloalkyl radicals, C _{6 ~ 30} of each other, C _{7 ~ 30} alkyl aryl radicals, C _{7 ~ 30} aryl-alkyl radical, or a C _{8 ~ 30} arylalkyl radical; Q and Q 'are the same or different and are each independently a halogen radical, a C _{1 ~ 20} alkyl radical, an alkylaryl radical of C _{2 ~ 20} alkenyl radicals, C _{6 ~ 30} aryl radicals, C _{7 ~ 30} of the , or aryl alkyl radical of C _{7 ~ 30} and, Q and Q 'may form a hydrocarbon ring of C _{1 ~ 20} taken together; B is an alkylene radical of C _{1 ~ 4,} a dialkyl silicon, germanium, alkyl phosphine, or amine, with two cyclopentadienyl based ligands, or a cyclopentadienyl ligand and JR ² _z share series combination _-y A leg tied by; R ² is a hydrogen radical, an aryl radical of C _{1 ~ 20} alkyl radicals, C _{2 ~ 20} alkenyl radicals, C _{6 ~ 30} aryl radicals, C _{7 ~ 30} alkylaryl radicals or C _{7 ~ 30} of the of the a ; J is a periodic table group 15 element or group 16 element; z is the oxidation number of the element J; y is the bond number of the J element; n and n 'are the same as or different from each other, and each independently represent a positive integer of 0 or more; r is an integer from 0 to 3; Y represents a hetero atom of O, S, N or P; A represents hydrogen or an alkyl radical of _{1 to 10} carbon atoms. The method of claim 6, wherein the hybrid supported metallocene catalyst a) preparing an activated supported metallocene catalyst by contacting a supported metallocene catalyst carrying at least one metallocene compound with a cocatalyst; And b) further supporting at least one metallocene compound different from the metallocene compound on the activated supported metallocene catalyst; Olefin-based polymer resin composition for pipes, characterized in that it is produced by a manufacturing method comprising a. The olefin polymer resin composition for pipe according to claim 1, wherein the olefin polymer is a homopolymer of an olefin monomer or a copolymer of an olefin monomer and an alpha olefin comonomer. The olefin-based polymer resin composition for pipes according to claim 1, wherein the density of the olefin-based polymer 1 is 0.920 to 0.960 g / cm ³ . The method of claim 1, wherein the olefin polymer resin composition for pipe is a heat stabilizer, antioxidant, UV absorber, light stabilizer, metal inert, filler, reinforcing agent, plasticizer, lubricant, emulsifier, pigment, optical bleach, flame retardant, antistatic agent And an olefin polymer resin composition for pipes, characterized in that it further comprises at least one additive selected from the group consisting of a blowing agent. The processing temperature of 170 degreeC or more at the time of the processing process by an extruder using the olefin type polymer resin composition for pipes of any one of Claims 1-10 characterized by the above-mentioned. The method of claim 11, wherein the extruder is pre-running for at least one hour in the processing process. Pipe manufactured by the manufacturing method of claim 11.

Images