KR101924121B1 - 1-butene based copolymer having excellent low temperature-high elongation property and processing method of them - Google Patents

Abstract

The present invention relates to a thermoplastic elastomer composition containing 60 to 92 mol% of units derived from 1-butene and 8 to 40 mol% of units derived from propylene, having a DSC melting point of 53 to 105 DEG C, a elongation at break of 400 to 800% 1-butene copolymer having a strength of 400 to 500 kgf / cm 2 and a breaking modulus of 2000 to 3500 kgf / cm 2 and a Ziegler-Natta type main catalyst, an aluminum-based co- Butene copolymer is prepared by bulk polymerization of 60 to 92 mol% of 1-butene and 8 to 40 mol% of propylene in a catalyst system constituting the propylene-based copolymer.

Description

TECHNICAL FIELD [0001] The present invention relates to a 1-butene-based copolymer having low-temperature-high elongation properties and a method for producing the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a thermoplastic elastomer composition containing 60 to 92 mol% of units derived from 1-butene and 8 to 40 mol% of units derived from propylene, having a DSC melting point of 53 to 105 DEG C, a elongation at break of 400 to 800% 1-butene copolymer having a strength of 400 to 500 kgf / cm 2 and a breaking modulus of 2000 to 3500 kgf / cm 2 and a Ziegler-Natta type main catalyst, an aluminum-based co- Butene copolymer is prepared by bulk polymerization of 60 to 92 mol% of 1-butene and 8 to 40 mol% of propylene in a catalyst system constituting the propylene-based copolymer.

Homopolybutene-1 is a semicrystalline polymer having excellent properties such as creep resistance, flexibility, abrasion resistance, and stretch uniformity, and has intermediate properties such as polyethylene and polypropylene. Homo polybutene-1, however, can not be used for pipes or limited film applications or as a modifier of polyolefins due to the limited physical properties of a DSC melting point of 125 ° C, elongation of 300%, breaking tensile strength of 380 kgf / cm 2 and elastic modulus of 5600 kgf / It is only being utilized.

On the contrary, the butene-1 copolymer is a polymer prepared by copolymerizing 1-butene and propylene, and has a low physical property in comparison with homopolybutene-1, and its production cost is low.

Butene-1 type copolymers which are currently commercially produced are generally produced by solution polymerization and are highly soluble in solvents and are required for production equipments such as high-cost devolatilizer for solvent removal. Further, it is difficult to obtain a very high level of stereoregularity due to the solubility of the solvent in the resin, and since the butene-1 copolymer having a low molecular weight is included, there is a fear of lowering the physical properties of the product.

The production method of the butene-1 copolymer reported in the current literature is as follows.

In European Patent Application No. 135,358 (Patent Document 1), a copolymer obtained by randomly copolymerizing 60 to 99 mol% of 1-butene and 1 to 40 mol% of propylene by applying a Ziegler-Natta type catalyst has a DSC melting point of 50 to 130 ° C , The elongation is 200 to 1000%, and the tensile strength at break is increased to 150 to 800 kg / cm < ^{2 &} gt ;. However, in Patent Document 1, it is difficult to deduce the DSC melting point with respect to the specific composition ratio of each monomer, and the ratio of the main catalyst and the cocatalyst is not presented. In other words, there is no consideration that the stereoregularity varies depending on the ratio of the main catalyst and the cocatalyst, and the DSC melting point and the mechanical properties are changed by the stereoregularity.

In International Patent Publication No. WO1994-005711 (Patent Document 2), a method of producing a butene-1 copolymer by copolymerizing 50 to 75% by weight of 1-butene and 25 to 50% by weight of propylene by applying a Ziegler-Natta type catalyst Lt; / RTI > In Patent Document 2, it is disclosed that the elongation at break is improved to 300% or more by changing the composition of the promoter, but the improvement effect is insignificant considering that the elongation of homopolybutene-1 is 300%.

U.S. Patent No. 3,332,921 discloses a copolymer obtained by copolymerizing 75 to 90% by weight of 1-butene and 10 to 25% by weight of propylene by applying it to a catalyst of Ti ₃ AlCl ₁₂ containing both main catalyst Ti and cocatalyst Al simultaneously the elongation at break of not less than 500%, breaking tensile strength, discloses said to have more than 210 kg _f / ㎠ characteristics. However, in Patent Document 3, Ti ₃ AlCl ₁₂ Catalysts are used, and the mechanical properties of the produced copolymers are not regular.

Polymer 19 (1978) 1222 to 1223 (Non-Patent Document 1) discloses that 1-butene and propylene are copolymerized by applying a TiCl ₃ -AlEt ₂ Cl catalyst, The DSC melting point tends to increase from 70 to 125 ° C as the content increases. However, Non-Patent Document 1 does not disclose the relationship between monomer content and elongation.

International Patent Publication No. WO2006-051035 (Patent Document 4) discloses a method for producing a copolymer containing 40 to 99 mol% of 1-butene and 1 to 60 mol% of propylene by applying a metallocene catalyst and solution polymerization . However, according to Patent Document 4, at a propylene content of 50 mol% or more, the DSC temperature is increased to 100 DEG C or higher, and a copolymer having polypropylene characteristics is prepared, which makes it difficult to exhibit tensile uniformity, which is an advantage of 1-butene- I have a problem. In addition, the metallocene catalyst is a monopoly supply due to the preemption of the patent rights of the catalyst manufacturer, which is formed at a high price, which makes it difficult to supply and supply the catalyst.

European Patent Publication No. 135,358 "novel random 1-butene copolymer" International Patent Publication No. WO994-005711 entitled "Amorphous 1-Butene / Propylene Copolymer Having High Tensile Strength" U.S. Patent No. 3,332,921 entitled "1-Butene-Propylene Copolymer" WO2006-051035 "Method for producing 1-butene / propylene copolymer"

 Polymer 19 (1978) 1222-1223 "Thermal and Mechanical Properties of Isoctatic Random Propylene-Butene-1 Copolymer"

The present invention relates to a copolymer comprising a 1-butene unit moiety and a propylene unit moiety in a monomer molar ratio (X) such that a DSC melting point (Y) calculated by the following formula (1) satisfies a range of 53 to 105 ° C, -1, which is improved in breaking elongation, breaking tensile strength, and breaking elastic modulus in comparison with that of the 1-butene copolymer.

[Equation 1]

Y = 199.9X ² - 238.5X + 123.4

(In the above formula (1), X represents the molar ratio of the monomer of propylene / 1-butene and Y represents the DSC melting point (占 폚)

In the present invention, the molar ratio (X) of the monomer of propylene and 1-butene is determined so that the DSC melting point (Y) calculated by the equation (1) satisfies the range of 53 to 105 ° C, Butene-based copolymers prepared by bulk polymerization of the above-mentioned copolymers.

It is another object of the present invention to provide a low temperature thermal adhesive film material or a polyolefin modifier containing the 1-butene-based copolymer.

In order to solve the above-mentioned problems, the present invention provides a thermoplastic resin composition comprising 60 to 92 mol% of a 1-butene unit as a monomer molar ratio (X) such that the DSC melting point (Y) And 10 to 40 mol% of propylene unit units,

The copolymer has a breaking elongation of 400 to 800%, a breaking tensile strength of 300 to 500 kgf / cm 2, and a breaking modulus of elasticity of 2000 to 3500 kgf / cm 2.

[Equation 1]

Y = 199.9X ² - 238.5X + 123.4

(In the above formula (1), X represents the molar ratio of the monomer of propylene / 1-butene and Y represents the DSC melting point (占 폚)

According to another aspect of the present invention, there is provided a catalyst system comprising (A) a main catalyst which is a Ti-supported catalyst of the Ziegler-Natta type, (B) an aluminum-based cocatalyst, and (C)

60 to 90% by mole of a 1-butene unit and 10 to 40% by mole of a propylene unit unit in a monomer molar ratio (X) such that the DSC melting point (Y) calculated by the above formula (1) And a method for producing a 1-butene-based copolymer by polymerization.

According to still another aspect of the present invention, there is provided a material for a low temperature thermal adhesive film comprising the 1-butene-based copolymer defined above.

According to still another aspect of the present invention, there is provided a polyolefin modifier comprising the 1-butene-based copolymer defined above.

The 1-butene-based copolymer provided by the present invention exhibits properties of improving stretchability, flexibility, and low-temperature processability as compared with homopolybutene-1. Thus, the 1-butene-based copolymer provided by the present invention is useful as a material for a low-temperature thermal adhesive film or as a modifier for improving physical properties of polyolefin, because it improves heat-seal productivity and uniform stretchability.

In addition, the 1-butene-based copolymer provided by the present invention is subjected to bulk polymerization and does not use any additional solvent, so that the proportion of the soluble fraction to the solvent is very small.

The present invention also provides a method for producing a 1-butene-based copolymer, which has a lower investment cost for a high-cost devolatilizer than a conventional method for producing a 1-butene copolymer using a solution polymerization method, It is possible to provide a high-purity 1-butene copolymer having a low degree of polymer volatilization and a high degree of polymerization.

1 is a graph showing the DSC melting point of a 1-butene-based copolymer prepared by a comparison of the molar ratio of monomers of 1-butene / propylene used in polymerization.

Unless otherwise specified, all numbers, values, and / or representations that express the amounts of components, reaction conditions, polymer compositions, and combinations used herein are intended to include those numbers It should be understood that in all cases the term "about" is to be construed as an approximation reflecting the various uncertainties of the measurement. Also, where a numerical range is disclosed in this specification, such a range is contiguous and includes all values from the minimum value of this range to the maximum value including the maximum value, unless otherwise indicated. Further, when such a range refers to an integer, all integers including the minimum value to the maximum value including the maximum value are included unless otherwise indicated.

In the present specification, when a range is described for a variable, it will be understood that the variable includes all values within the stated range including the end points described in the range. For example, a range of "5 to 10" may include any subrange, such as 6 to 10, 7 to 10, 6 to 9, 7 to 9, etc., as well as values of 5, 6, 7, 8, 9, And will also be understood to include any value between integers that are reasonable within the scope of the stated ranges such as 5.5, 6.5, 7.5, 5.5 to 8.5 and 6.5 to 9, and so on. Also, for example, a range of "10% to 30%" may range from 10% to 15%, 12% to 12%, as well as all integers including values of 10%, 11%, 12%, 13% And any arbitrary integer within the range of ranges described, such as 10.5%, 15.5%, 25.5%, and the like, including any subranges such as 18%, 20%

The 1-butene-based copolymer according to the present invention has a monomer molar ratio (X) such that the DSC melting point (Y) calculated by the following formula (1) satisfies the range of 50 to 100 캜: 60 to 92 mol% And 8 to 40 mol% of propylene unit parts.

[Equation 1]

Y = 199.9X ² - 238.5X + 123.4

(In the above formula (1), X represents the molar ratio of the monomer of propylene / 1-butene and Y represents the DSC melting point (占 폚)

The 1-butene-based copolymer according to the present invention has improved physical properties as compared to a polybutene homo polymer. The DSC melting point (Y) calculated by the above formula (1) is 53 to 105 ° C The elongation at break is 400 to 800%, the breaking tensile strength is 300 to 500 kgf / cm 2, and the breaking elastic modulus is 2000 to 3000 kgf / cm 2.

The above formula (1) is derived through a bulk polymerization method, and its derivation process will be described in detail in the following preparation examples.

The present invention also features a process for producing a 1-butene propylene copolymer. The method for producing a 1-butene propylene copolymer according to the present invention is characterized in that in a catalyst system composed of (A) a Ziegler-Natta type Ti supported catalyst, (B) an aluminum based promoter and (C) a silane based promoter, 60 to 92% by mole of 1-butene unit and 8 to 40% by mole of propylene unit unit in a monomer molar ratio (X) such that the DSC melting point (Y) calculated by the above formula (1) Followed by polymerization.

The process for producing the copolymer of the present invention is characterized in that it is carried out by the bulk polymerization method instead of the solution polymerization method. The present commercialized butene-1 copolymer is produced by the solution polymerization method, so that the solubility of the solvent in the resin remains in the resin, so that the stereoregularity is limited. Further, in order to remove the solvent, Equipment is required. However, in the present invention, the bulk polymerization process using a monomer as a reactant or a polymerization solvent is carried out without using a polymerization solvent to obtain a high-purity 1-butene propylene copolymer having a high degree of polymerization.

The method for producing the copolymer according to the present invention will be described in more detail as follows.

In the method for producing a copolymer of the present invention, 60 to 90 mol% of 1-butene and 10 to 40 mol% of propylene are used as a monomer molar ratio (X) in which the DSC melting point (Y) Mol%.

As shown in FIG. 1, the DSC melting point (Y) gradually decreases as the mole ratio of the monomer (X) increases. When the mole ratio of the monomer (X) is about 0.54, the DSC melting point (Y) Deg.] C, and the DSC melting point (Y) gradually increases as the molar ratio of the monomer (X) increases. In other words, in the monomer composition composed of 1-butene and propylene, the DSC melting point (Y) decreased from 125 ° C to 50 ° C in the section where the content of 1-butene was 100 mol% to 65 mol% Is less than 65 mol%, the DSC melting point (Y) gradually increases.

Since the present invention aims to provide a 1-butene-based copolymer having a low-temperature and high-elongation characteristic, a monomer composition ratio having a DSC melting point (Y) of 53 to 105 ° C is obtained. Specifically, 1-butene and propylene are polymerized in such a manner that the molar ratio (X) of the propylene / 1-butene monomer corresponding to the target DSC melting point is in the range of 0.11 to 0.66.

That is, when the molar ratio (X) of the monomer of propylene / 1-butene is 0.11 to 0.66, the DSC melting point (Y) has a low temperature characteristic of 53 to 105 ° C while the elongation at break and tensile strength at break increase, The effect of improvement can be obtained.

On the other hand, when the propylene content is less than 10 mol%, that is, when the molar ratio (X) of propylene / 1-butene monomer is less than 0.11, the DSC melting point of the synthesized copolymer exceeds 100 ° C., The elongation, the breaking tensile strength and the breaking elastic modulus remain at the homopolybutene-1 level.

Therefore, in order to prepare a 1-butene-based copolymer suitable for use as a material for a low temperature-high elongation film, a monomer content range satisfying the DSC melting point calculated from the formula 1 proposed by the present invention is 1-butene and propylene Is preferably polymerized.

In the process for producing a copolymer according to the present invention, a catalyst system composed of (A) a Ziegler-Natta type Ti-supported catalyst, (B) an aluminum-based co-catalyst and (C) a silane-based co-

The (A) Ziegler-Natta type main catalyst is a catalyst used in an olefin polymerization process, and may include a titanium (Ti) active component and a halogen ligand, a carrier or a ligand and a carrier at the same time. The main catalyst of the (A) Zieger-Natta type may be a catalyst in which a titanium (Ti) active metal is supported on a carrier containing magnesium (Mg). Specifically, the catalyst may be a catalyst in which a titanium (Ti) active metal is supported on a magnesium halide carrier. The main catalyst (A) of the Ziegler-Natta type may be used in the range of 0.1 to 10 ppm based on the total weight of monomers comprising 1-butene and propylene. If the amount of the main catalyst of the (A) Ziegler-Natta type is less than 0.1 ppm, the catalyst activity is low and the polymerization reaction is difficult to proceed effectively. If the amount is more than 10 ppm, excessive use of the catalyst And the activity of the copolymer in the bulk polymerization is too high, which is a problem in resin transfer in commercial reaction systems.

The catalyst functions as a polymerization promoter for causing coordination polymerization with titanium (Ti) of the aluminum-based co-catalyst (B) main catalyst and also acts to remove catalyst poison by reacting with oxygen molecules which are impurities contained in the monomers. The aluminum-based co-catalyst (B) may be an aluminum compound in which a hetero atom selected from a halogen atom and a C ₁ -C ₁₀ alkyl group is bonded. The aluminum-based co-catalyst (B) specifically includes diethylaluminum chloride (DEAC), ethylaluminum dichloride (EADC), dinormalbutylaluminum chloride (DNBAC), diisobutylaluminum chloride (DIBAC) ), Triisobutyl aluminum (TIBA), trinormal hexyl aluminum (TNHA), trinornal octyl aluminum (TNOA) and trinormaldecyl aluminum (TNDA) But is not limited thereto. The aluminum-based co-catalyst (B) may be used in a range of 50 to 500 molar ratio with respect to the Ti content of the main catalyst (A). When the content of (B) aluminum-based co-catalyst is less than 50 molar ratio with respect to the amount of Ti, the conversion of raw materials is lowered because aluminum does not play a role for promoting co-catalysis and removal of catalyst poisoning in coordination polymerization. On the other hand, if the content of (B) aluminum-based co-catalyst exceeds 500 molar ratio with respect to the amount of Ti, the addition effect is insufficient due to an increase in the amount of Ti.

The silane-based promoter (C) serves to increase the stereoregularity of the copolymer. The (C) a silane-based co-catalyst is C ₁ ~ C ₁₀ alkyl group, C ₁ ~ C ₁₀ Al kokgi and C ₆ ~ C the two kinds or more selected from ₁₂ aryl group is bonded mono-, di-or tri selected from alkoxysilane compounds May be used. The silane-based co-catalyst (B) is specifically exemplified by diphenyldimethoxysilane, phenyltrimethoxysilane, isobutylmethoxysilane, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, etc. , And the present invention is not limited thereto. The (C) silane co-catalyst may be used in a range of 1 to 100 molar ratio relative to the (Ti) content of the main catalyst (A). When the content of the silane co-catalyst is less than 1 molar ratio with respect to the Ti content, the stereoregularity is lowered and the crystallinity is lowered, thereby reducing the mechanical properties. On the other hand, if the content of the (C) silane co-catalyst exceeds 100 molar ratio with respect to the Ti content, the effect of addition due to the increase in the amount of Ti is insufficient.

Further, in constituting the catalyst system of the present invention, the conversion ratio, stereoregularity and molecular weight of the copolymer synthesized by the content ratio of (B) the aluminum-based co-catalyst and (C) the silane-based co-catalyst may be changed. Preferably, the molar ratio of (B) / (C) is maintained in the range of 5 to 20 as a cocatalyst. If the molar ratio of (B) / (C) is less than 5, the stereoregularity becomes higher, but the concentration of the aluminum-based co-catalyst is low and the coordination polymerization conversion rate is lowered and it may be ineffective to remove the catalyst poison. On the other hand, if the molar ratio of (B) / (C) exceeds 50, the Ti active sites are sufficiently activated and the effect of maintaining the catalytic activity due to the catalyst poisoning can be obtained. However, It is difficult to obtain a coalesced polymer and a low molecular weight polymer is produced, resulting in tackiness.

In the method for producing a copolymer of the present invention, hydrogen gas is introduced as a molecular weight regulator. In the present invention, the reaction pressure can be controlled within a range of 5 to 50 bar by introducing an inert gas together with the hydrogen gas. It is not desirable to keep the reaction pressure higher than 50 bar, which is inefficient compared to facility investment. Therefore, in the present invention, by injecting an inert gas together with hydrogen gas and applying a pressure higher than the gas-liquid equilibrium pressure at the polymerization temperature, the activity of the polymerization reaction can be greatly enhanced. Any inert gas may be used as long as it does not affect the polymerization reaction. Specifically, at least one inert gas selected from the group consisting of nitrogen, helium, and argon may be used.

In the method for producing a copolymer of the present invention, the reaction temperature is maintained at 20 ° C or higher, specifically 20 ° C to 100 ° C. If the polymerization reaction temperature is lower than 20 ° C, the reaction at low activation is inefficient. If the polymerization reaction temperature exceeds 100 ° C, the heat input may not be effective and the reaction activity is not affected.

The 1-butene propylene copolymer produced through the above polymerization method had a DSC melting point of 53 to 105 ° C, a elongation at break of 400 to 800%, a breaking tensile strength of 300 to 500 kgf / cm 2, a breaking modulus of 2000 ~ 3500 ㎏f / ㎠ with low temperature and high elongation characteristics.

Therefore, the 1-butene propylene copolymer of the present invention is useful as a material for a low-temperature thermal adhesive film and a polyolefin modifier since it has properties of improving stretchability, flexibility and low-temperature melting point as compared with homopolybutene-1.

The present invention will now be described in more detail with reference to the following examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited thereto.

[Example]

Preparation Yes. The function formula derivation process of Equation (1)

A 3 L volumetric stainless autoclave was purged sufficiently with nitrogen to remove oxygen and moisture that could affect catalyst poisons. As the polymerization monomer, 1-butene and propylene were prepared so that the total amount of the monomers was 200 g, and they were weighed so that the molar ratio of 1-butene / propylene monomer was 0, 0.08, 0.15, 0.33 or 0.57 as shown in Table 1 . For example, in order to obtain a molar ratio of 1-butene / propylene monomer of 0.57, 160 g of 1-butene monomer and 40 g of propylene monomer were prepared.

The catalyst system consisted of (A) a main catalyst which was a Ti-supported catalyst of the Ziegler-Natta type, (B) an aluminum based promoter and (C) a silane based promoter. Specifically, (A) the main catalyst was quantitatively adjusted to have a Ti content of 0.17 ppm with respect to the total weight of the monomers, and dispersed in 100 mL of hexane. Triethylaluminum was prepared as the aluminum-based co-catalyst (B), and diisomethoxysilane was prepared as the silane-based co-catalyst (C). (A) Based on the Ti content of the main catalyst, triethylaluminum and diisopropylmethoxysilane were prepared in a molar ratio of 1: 300: 20, with 3.8 g of triethylaluminum and 0.0412 g of diisomethoxysilane Respectively. The molar ratio of the (B) aluminum-based co-catalyst / (C) silane-based co-catalyst was adjusted to 15 and prepared.

The prepared (B) aluminum-based co-catalyst was dispersed in 100 mL of hexane and then charged into the autoclave reactor together with the (C) silane co-catalyst and the prepared monomer. At this time, the mixture was stirred at a stirring speed of 150 rpm at room temperature using a mechanical stirrer. Then, 6 L of hydrogen gas was added, stirred for about 5 minutes, and then the internal temperature of the reactor was raised from room temperature to 50 캜.

Then, the main catalyst (A) prepared above was charged into the reactor, and a polymerization reaction was carried out at a polymerization temperature of 70 ° C for 1 hour under the pressure of the internal pressure of the reactor of 17 bar by injecting nitrogen inert gas. Upon completion of the polymerization, a polymer was obtained, and ethanol and an antioxidant were added thereto to remove catalyst residues and prescription of an antioxidant. The received resin was dried in a vacuum oven. The DSC melting point (Tm ₁ ) of the prepared 1-butene copolymer was measured at 10 ° C / min.

As shown in the following Table 1, a 1-butene copolymer was prepared by the polymerization method as described above while varying the molar ratio of 1-butene / propylene monomer, and the DSC melting point of the prepared 1-butene copolymer was measured.

division Propylene / 1-butene molar ratio DSC melting point (占 폚) of the copolymer One 0 125 2 0.10 100 3 0.33 68 4 0.57 59 5 0.89 66 1) mol% based on the total amount of 1-butene and propylene
2) The main catalyst (A) had a titanium content of 0.17 ppm
3) The molar ratio of main catalyst (A) / cocatalyst (B) / cocatalyst (C) was 1: 300: 20
4) Reaction temperature 70 ° C, reaction pressure 17 bar, hydrogen gas 6L, polymerization time 1 hour

In Table 1, the monomer ratio of 1-butene / propylene was plotted on the X-axis, and the DSC melting point of the copolymer was plotted on the Y-axis to obtain the graph of FIG.

From the graph of Fig. 1, the following equation (1) is derived.

[Equation 1]

Y = 199.9X ² - 238.5X + 123.4

(In the above formula (1), X represents the molar ratio of the monomer of propylene / 1-butene and Y represents the DSC melting point (占 폚)

Example 1. Preparation of 1-butene-based copolymer

A 3 L volumetric stainless autoclave was purged sufficiently with nitrogen to remove oxygen and moisture that could affect catalyst poisons. 160 g of 1-butene monomer and 40 g of propylene monomer were prepared so that the molar ratio of 1-butene / propylene as the reactant was 0.57.

Catalyst system has (A) a Ziegler-magnesium chloride as main catalyst of the shown type (MgCl ₂₎ using a titanium (Ti) an active metal-carrying catalyst on the carrier, and triethylaluminum as an aluminum-based co-catalyst (B) aluminum (AlCl ₃ ) Was used, and (C) diisopropylmethoxysilane was used as a silane-based co-catalyst. Specifically, (A) the main catalyst was quantitatively determined so that Ti became 0.17 ppm relative to the total weight of the monomers and dispersed in 100 mL of hexane. (A) The aluminum-based co-catalyst (B) and the silane-based co-catalyst were prepared to have a molar ratio of 1: 300: 20 based on the Ti content of the main catalyst. 3.8 g of triethyl aluminum, 0.0412 < RTI ID = 0.0 > g < / RTI > The molar ratio of the (B) aluminum-based co-catalyst / (C) silane-based co-catalyst was adjusted to 15 and prepared.

The prepared (B) aluminum-based co-catalyst was dispersed in 100 mL of hexane and then charged into the autoclave reactor together with the (C) silane co-catalyst and the prepared monomer. At this time, the mixture was stirred at a stirring speed of 150 rpm at room temperature using a mechanical stirrer. Then, 6 L of hydrogen gas was added, stirred for about 5 minutes, and then the internal temperature of the reactor was raised from room temperature to 50 캜.

Then, the main catalyst (A) prepared above was charged into the reactor, and a polymerization reaction was carried out at a polymerization temperature of 70 ° C for 1 hour under the pressure of the internal pressure of the reactor of 17 bar by injecting nitrogen inert gas. Upon completion of the polymerization, a polymer was obtained, and ethanol and an antioxidant were added thereto to remove catalyst residues and prescription of an antioxidant. The received resin was dried in a vacuum oven.

Examples 2 to 7 and Comparative Examples 1 to 7

The polymerization was carried out in the same manner as in Example 1 to prepare a polymer, which was carried out under the conditions shown in Table 2 below.

division Propylene / 1-butene (molar ratio) The composition of the catalyst system (molar ratio) Polymerization conditions Ti: (B) :( C) (B) / (C) Temperature
(° C) pressure
(bar)
room
city
Yes One 0.57 1: 300: 20 15 70 17 2 0.33 1: 300: 20 15 70 17 3 0.10 1: 300: 20 15 70 17 4 0.57 1: 300: 30 10 70 17 5 0.57 1: 300: 60 5 70 17 6 0.57 1: 300: 20 15 50 12 7 0.57 1: 300: 20 15 80 19
ratio
School
Yes One 0.08 1: 300: 20 15 70 17 2 0.89 1: 300: 20 15 70 17 3 0.57 1: 100: 25 4 70 17 4 0.57 1: 300: 12 25 70 17 5 0.57 1: 40: 2.7 15 30 17 6 1-butene 1: 300: 20 15 70 17 7 Propylene 1: 300: 20 15 70 17

Test example. Evaluation of physical properties of polymer

The polymers prepared according to Examples 1 to 7 and Comparative Examples 1 to 7 were measured for physical properties by the following evaluation methods, and the results are shown in Tables 3 and 4, respectively.

≪ Evaluation method of physical properties of polymer &

(1) Stereoregularity: Measured by ¹³ C NMR

(2) Melt Index: Measured according to ASTM D1238

(3) Tensile Strength at Break: Measured according to ASTM D638

(4) Elongation at Break: Measured according to ASTM D638

(5) Elasticity or Young's Modulus: Measured according to ASTM D638

(6) Melting Point: Measured according to ASTM D3418

Properties Example One 2 3 4 5 6 7 Yield (kg / g_ _cat. ) 3.2 4.5 4.5 2.6 2 2.8 3 Stereoregularity (%) 95.1 93.95 94.5 95.8 96 94.2 94.7 The melt index (g / 10 min) 4 4 4 4 4 4 4 Breaking tensile strength
(kgf / cm2) 416 430 460 420 430 430 450 Elongation (%) 750 680 500 760 750 750 755 Elastic modulus (kgf / ㎠) 2121 2800 3400 2230 2150 2300 2210 DSC melting point (占 폚) 58 68 100 57 59 58 59

Properties Comparative Example One 2 3 4 5 6 7 Yield (kg / g_ _cat. ) 4 4 0.5 3.2 ND 2.8 2.5 Stereoregularity (%) 95 95 96 87 ND 96 94 The melt index (g / 10 min) 4 4 4 4 ND 4 4 Tensile strength (kgf / cm2) 350 340 ND 270 ND 380 350 Elongation (%) 320 700 ND 720 ND 300 150 Elastic modulus (kgf / ㎠) 5100 4000 ND 570 ND 5660 15000 DSC melting point (占 폚) 110 66 59 58 ND 125 160

Examples 1 to 7 are 1-butene-based copolymers produced under the polymerization reaction conditions proposed by the present invention. As the propylene / 1-butene monomer molar ratio decreases to 0.57, 0.33 and 0.10, the DSC melting point becomes 68 Lt; RTI ID = 0.0 > 58 C. < / RTI > The homopolybutene-1 of Comparative Example 6 had a DSC melting point of 125 ° C, elongation of 300%, tensile strength of 380 kgf / cm 2 and elastic modulus of 5660 kgf / cm 2, It was confirmed that the tensile strength was improved to less than 100 ° C, elongation 500 to 760, tensile strength 416 to 460 kgf / cm 2, and elastic modulus 2121 to 3400 kgf / cm 2.

Examples 5 and 6 are 1-butene-based copolymers produced under catalytic conditions in which the content ratio of the (B) aluminum-based co-catalyst and (C) the silane-based co-catalyst (B) was changed. According to Examples 1 to 7, when the co-catalyst molar ratio of (B) / (C) is in the range of 5 to 20, it can be understood that a copolymer having DSC melting point and mechanical properties within the range required by the present invention can be produced .

On the contrary, Comparative Examples 1 and 2 are copolymers produced under the conditions of propylene / 1-butene monomer molar ratios of 0.08 and 0.89, respectively. Comparative Example 1 was a copolymer having a propylene / 1-butene molar ratio of 0.08 and a propylene content of less than 8 mol% in a small amount, and the DSC melting point was decreased from 125 캜 to 110 캜 as compared with Comparative Example 6 (homopolybutene-1) , The elongation was increased from 300% to 320%, and the elastic modulus was decreased from 5660 to 5100 kgf / cm 2, but the improvement effect was insignificant, indicating that the homopolybutene-1 characteristics were maintained. Comparative Example 2 was a copolymer having a propylene / 1-butene molar ratio of 0.89 and a propylene content exceeding 40 mol%, and had a high elastic modulus (4000 kgf / cm 2), which is a property of the propylene copolymer And the elastic modulus reduction property, which is an advantage of the butene-1 copolymer, was not found.

In Comparative Examples 3 and 4, copolymers were prepared under the conditions that the molar ratio of the co-catalysts (B) / (C) was 4 or 25. According to Comparative Example 3, the yield of the copolymer was reduced to 0.5 kg / g-cat in the catalyst system having the co-catalyst molar ratio of (B) / (C) of 4, and the amount of the copolymer capable of measuring mechanical properties could not be obtained. According to Comparative Example 4, the DSC melting point of the catalyst system of (B) / (C) was 25, which was satisfactory at a temperature of 58 캜, but the tacticity was 270 kgf / cm 2 and the modulus of elasticity was 1500 kgf / .

In Comparative Example 5, since a small amount of the (B) aluminum-based co-catalyst was contained in an amount of less than 40 molar ratio with respect to the Ti content, the reaction rate was low and the yield of the catalyst was low due to the low efficiency of catalyst poisoning and co- There is a limit.

In Comparative Example 6, homopolybutene-1 was produced using 1-butene as a monomer while maintaining the polymerization conditions of Example 1, and Comparative Example 7 was an example in which homopolypropylene was produced using propylene as a monomer to be. Comparative Example 6 and Comparative Example 7 show that the DSC melting point is high and physical properties such as elongation at break, tensile strength at break, and modulus of rupture elasticity are largely out of the category proposed by the present invention.

Claims (11)

delete (A) Ziegler-Natta type Ti supported catalyst, (B) an aluminum-based cocatalyst, and (C) a silane-based cocatalyst,
60 to 92 mol% of a 1-butene unit and 8 to 40 mol% of a propylene unit unit at a monomer molar ratio (X) such that the DSC melting point (Y) calculated by the following formula (1) Bulk manufactured in bulk,
The main catalyst (A) of the Ziegler-Natta type constituting the catalyst system contains a Ti content in the range of 0.1 to 10 ppm based on the total weight of the propylene / 1-butene monomers,
The (B) aluminum-based co-catalyst is contained in a range of 50 to 500 molar ratio with respect to the Ti content,
The (C) silane co-catalyst is contained in a range of 1 to 100 molar ratio relative to the Ti content,
Wherein the molar ratio of (B) / (C) is in the range of 5 to 18 in the (B) aluminum-based co-catalyst and the (C) silane-based co-catalyst.
[Equation 1]
Y = 199.9X ² - 238.5X + 123.4
(In the above formula (1), X represents the molar ratio of the monomer of propylene / 1-butene and Y represents the DSC melting point (占 폚)
3. The method of claim 2,
Wherein the molar ratio (X) of the propylene / 1-butene monomer is in the range of 0.11 to 0.66.
3. The method of claim 2,
Wherein the bulk polymerization is carried out by using a monomer of 1-butene and propylene as a reaction or polymerization solvent.
3. The method of claim 2,
Wherein the bulk polymerization is performed at a temperature of 20 ° C to 100 ° C.
3. The method of claim 2,
Wherein the bulk polymerization is carried out at a reaction pressure of 5 to 50 bar by introducing at least one inert gas selected from the group consisting of nitrogen, helium and argon, together with hydrogen gas, .
delete delete 3. The method of claim 2,
From 60 to 92 mol% of units derived from 1-butene and from 8 to 40 mol% of units derived from propylene;
A DSC melting point of 53 to 105 캜;
The elongation at break is 400 to 800%;
A breaking tensile strength of 300 to 500 kgf / cm 2;
And a breaking modulus of elasticity of 2000 to 3500 kgf / cm < 2 >.
delete delete

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