KR101496711B1 - Polybutene-1 polymer composition and molded object formed using the same and method of producing polybutene-1 polymer composition - Google Patents

Abstract

The present invention relates to a polybutene-1 polymer composition with outstanding rigidity and moldability, a molded body by molding the same and a manufacturing method of polybutent-1 polymer and, more specifically, a polybutene-1 polymer composition including (a) a polybutene-1 polymer whose soluble fraction content is 1-10 wt% in xylene at room temperature and melt flow rate (MFR) is 1 to 5 g/10 min in conditions of ASTM D-1238, 190 degree Celsius and 2.16kg; and (b) polybutent-1 polymer whose soluble fraction content is 10-30 wt% in xylene at room temperature and melt flow rate (MFR) is 0.1 to 0.5 g/10 min in conditions of ASTM D-1238, 190 degree Celsius and 2.16kg.

Description

TECHNICAL FIELD The present invention relates to a polybutene-1 polymer composition, a molded article produced by molding the same, and a process for producing a polybutene-1 polymer composition. BACKGROUND ART [0002] POLYBUTENE-1 POLYMER COMPOUNDS AND METHOD OF PRODUCING POLYBUTENE-

The present invention provides a polybutene-1 polymer composition excellent in rigidity and molding processability, a molded article produced by molding the same, and a method for producing a polybutene-1 polymer composition.

Generally, the polybutene-1 polymer is a semi-crystalline polymer having 1-butene as a monomer, and is a high molecular weight polyolefin having general physical properties similar to those of polyethylene and polypropylene.

The polybutene-1 polymer is excellent in pressure resistance, creep resistance, abrasion resistance and rigidity, and has excellent stability such as long-term durability even at a high temperature. In addition, a molded article can be easily produced from a polybutene-1 polymer by using a processing machine such as extrusion, injection, or blow molding, which has been applied to conventional polyolefins. As described above, the polybutene-1 polymer has excellent physical properties and is thus suitably used as a pipe material for water supply and hot water supply, and thus its utility value is very high.

In this connection, Korean Unexamined Patent Publication No. 2009-0043545 discloses a 1-butene / propylene copolymer composition having a molecular weight distribution (Mw / Mn) of 4 or less and a stereoregularity of 80% or more. The above technique has high stereoregularity, has a high crystallinity, and is excellent in rigidity and impact resistance, but has a narrow molecular weight distribution of 4 or less and increases the shear rate. Accordingly, the development of a polybutene-1 polymer which is excellent in stiffness inherent to the polybutene-1 polymer and easy in molding processability when manufactured into a pipe using a polymer is desired.

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art described above, and it is an object of the present invention to provide a polybutene-1 polymer having two kinds of polybutene-1 polymers having different stereoregularity and melt viscosity, To provide a polymer composition and a method for producing the same.

Another object of the present invention is to provide a molded article produced by molding the polybutene-1 polymer composition.

In order to attain the above object, the present invention provides a process for producing a polylactic acid copolymer, which comprises 1 to 10% by weight of a fraction soluble in xylene at room temperature and 1 to 5 g / 10 min of a melt flow rate (ASTM D-1238, (ASTM D-1238, temperature 190 占 폚, load 2.16 kg) is in the range of 0.1 to 0.5% by weight, the content of the fraction soluble in xylene at room temperature is 10 to 30% g / 10 min. The polybutene-1 polymer composition according to claim 1, wherein the polybutene-1 polymer (b) is a polybutene-1 polymer.

The polymer composition may be mixed with 10 to 50% by weight of the polybutene-1 polymer (a) and 50 to 90% by weight of the polybutene-1 polymer (b).

The polymer composition may have a fractional content difference (DELTA) of 5 to 20 and a melt flow rate difference (DELTA) of 1 to 5 in the polymer (a) and the polymer (b).

The polymer composition may have a flowability ratio (S / R) of 4.5 or more in the following formula (1).

[Equation 1]

Flow ratio (S / R) = MIP / MIE

(Wherein MIP is a melt flow rate measured at ASTM D-1238, temperature 190 캜, load 5 kg, MIE is melt flow rate measured at ASTM D-1238, temperature 190 캜, load 2.16 kg)

The polybutene-1 polymer (a) and the polybutene-1 polymer (b) may be each independently a butene-1 homopolymer.

Also disclosed is a molded article produced by molding the polybutene-1 polymer composition.

The molded article may have a yield tensile strength of 17 to 19 MPa, a tensile tensile strength of 31 to 34 MPa, and a tensile elongation at break of 280 to 297%.

The formed body may be a pipe.

(A) the first reactor has a fraction of xylene-soluble fraction at room temperature of 1 to 10% by weight and a melt flow rate (ASTM D-1238, temperature 190 캜, load of 2.16 kg) of 1 (B) the content of xylene-soluble fraction at room temperature in the second reactor is 10 to 30% by weight and the melt flow rate (ASTM D (B), wherein the polybutene-1 polymer (b) is 0.1 to 0.5 g / 10 min, the temperature is 190 ° C and the load is 2.16 kg; and (C) (a) 10 to 50% by weight of the polybutene-1 polymer and 50 to 90% by weight of the polybutene-1 polymer (b) prepared in the second reactor .

The mixer may be connected in series with each of the first reactor and the second reactor.

The polybutene-1 polymer composition of the present invention has excellent stiffness and ease of molding processability of a polymer composition by using two kinds of polybutene-1 polymers having different stereoregularity and melt viscosity. Therefore, the above-mentioned polybutene-1 polymer composition can be usefully used for a pipe material for hot water and water supply.

The present invention provides a polybutene-1 polymer composition excellent in rigidity and molding processability.

Hereinafter, the present invention will be described in detail.

The polybutene-1 polymer composition of the present invention includes two types of polybutene-1 polymer (a) and polybutene-1 polymer (b) having different stereoregularity and melt viscosity.

Specifically, the polybutene-1 polymer composition preferably contains 1 to 10% by weight of a fraction soluble in xylene at room temperature and 1 to 5 g of a melt flowrate (ASTM D-1238, temperature 190 캜, load 2.16 kg) (ASTM D-1238, temperature 190 占 폚, load 2.16 kg) is 0.1 to 10 minutes, and the content of the fraction soluble in xylene at room temperature is 10 to 30% by weight and the melt flow rate To 0.5 g / 10 min. Of the polybutene-1 polymer (b).

The content of the fraction soluble in xylene at room temperature is preferably 1 to 10% by weight, more preferably 1 to 3% by weight, in the polymer (a) which is a constituent component of the polybutene-1 polymer composition. The fraction content corresponds to 90 to 99% by weight, more preferably 97 to 99% by weight, of the stereoregularity.

The fraction soluble in xylene can be obtained by applying a commonly known xylene soluble (XS) method, and the stereoregularity of the polymer (a) can be known indirectly through the thus obtained fraction content.

Specifically, when the polymer (a) is dissolved in xylene to be refluxed and cooled to room temperature, the crystalline component is precipitated, the amorphous component remains in the solution state, and the remaining solution is expressed as% XS will be.

The polymer (a) preferably has a melt flow rate MFR (ASTM D-1238, temperature 190 占 폚, load 2.16 kg) of 1 to 5 g / 10 min. More preferably 1.8 to 4.6 g / 10 min.

Specifically, the polymer (a) is heated to 190 DEG C, the piston to be subjected to a load of 2.16 kg is put in position, and then the orifice (inner diameter: 2.09 mm, length: 8 mm) for a certain period of time, and converting the weight of the polymer to the amount of passage for 10 minutes.

As described above, when the melt flow rate MFR (ASTM D-1238, temperature 190 캜, load 2.16 kg) of the polymer (a) is in the range of 1 to 5 g / 10 min, it has a high MFR value (low molecular weight) Is lower than that of the polybutene-1 polymer (b) to be described later, the molding processability of the polymer composition can be improved, but the rigidity is lowered. In order to solve this problem, the present invention can provide a polybutene-1 polymer composition which is excellent in rigidity and advantageous in moldability by controlling the fraction of the polymer (a) soluble in xylene to 1 to 10% by weight.

The content of the fraction soluble in xylene at room temperature is preferably 10 to 30% by weight, more preferably 10 to 20% by weight, in the polymer (b) which is a constituent component of the polybutene-1 polymer composition. The fractional content corresponds to 70 to 90% by weight, more preferably 80 to 90% by weight, of the stereoregularity.

The polymer (b) preferably has a melt flow rate MFR (ASTM D-1238, temperature 190 캜, load 2.16 kg) of 0.1 to 0.5 g / 10 min. More preferably 0.12 to 0.21 g / 10 min.

As described above, the polymer (b) has a low MFR value (high molecular weight) when the melt flow rate MFR (ASTM D-1238, temperature 190 캜, load 2.16 kg) is in the range of 0.1 to 0.5 g / Upon mixing with the polybutene-1 polymer (a), the stiffness of the polymer composition can be improved, but the melt viscosity is high and a problem of lowered molding processability arises. In order to solve this problem, the present invention can provide a polymer composition having excellent rigidity and favorable molding processability of a polymer composition by controlling the fraction of the polymer (b) soluble in xylene to 10 to 30 wt%.

The measurement of fraction content and MFR soluble in xylene is the same as the measurement of the polymer (a) described above, so a detailed description thereof will be omitted.

The fractional difference (DELTA) of the polymer (a) and the polymer (b) is 5 to 20, and the difference (DELTA) of the melt flow rate may be 1 to 5. When the difference in fractional content and the difference in melt flow rate are out of the above range, it may be difficult to obtain a polybutene-1 polymer composition having both rigidity and moldability.

As described above, the polybutene-1 polymer composition according to the present invention has the problem of lowering the stiffness due to the polymer (a) and lowering the molding processability due to the polymer (b) The physical properties of the polymer composition can be greatly improved.

Further, in relation to the excellent rigidity and molding processability of the polybutene-1 polymer composition, the polymer composition may contain 10 to 50% by weight of the polybutene-1 polymer (a) and 50 to 90% by weight of the polybutene- It is preferable to mix them.

The polybutene-1 polymer composition including the two kinds of polymers (a) and (b) having different stereoregularity and melt viscosity can satisfy the flow ratio (S / R) of the following formula have.

[Equation 1]

Flow ratio (S / R) = MIP / MIE

(Wherein MIP is a melt flow rate measured at ASTM D-1238, temperature 190 캜, load 5 kg, MIE is melt flow rate measured at ASTM D-1238, temperature 190 캜, load 2.16 kg)

The flow ratio (S / R) means the MFR ratio measured under different conditions. The present invention derives the range of the flow ratio as described above by controlling the MFR ratio of the polymer composition so that the molded article can exhibit excellent appearance and long-term durability.

The flowability ratio preferably satisfies a range of 4.5 or more, more preferably 4.7 to 5.1. When the flowability ratio is less than 4.5, the molding processability is very sensitive to the conditions, and thus the surface of the molded article tends to be defective and the pressure resistance is lowered.

The polybutene-1 polymer composition according to the present invention may contain, in addition to the above polymers (a) and (b), additives generally used in the art within the range not to impair the effect of the present invention.

The additive may be an antioxidant, an ultraviolet absorber, a bactericide, a rust inhibitor, a lubricant, a filler, a pigment, a heat-resistant stabilizer, and the like.

In particular, the antioxidant is used for improving the durability of the molded article produced by molding the resin composition, such as heat aging resistance and resistance to chlorine, and for example, antioxidants such as phenolic compounds and phosphorus compounds can be used.

The polybutene-1 polymer composition may be formed into a molded article by extrusion, injection, or blow molding.

The molded article thus produced has a yield tensile strength of 17 to 19 MPa, a tensile tensile strength of 31 to 34 MPa, and a tensile elongation at break of 280 to 297%, which is excellent in rigidity.

Further, when the molded body is a pipe, the roughness of the inner and outer surfaces of the pipe can be prevented, and the appearance and formability of the pipe can be improved.

At this time, in order to use the polybutene-1 polymer composition as a material of the pipe, the polymers (a) and (b) are preferably homopolymers.

The polybutene-1 polymer composition according to the present invention can be produced by independently polymerizing the polymers (a) and (b), respectively, and then physically mixing the polymers (a) and (b) in a subsequent step.

Specifically, the method for producing a polybutene-1 polymer composition according to the present invention comprises the steps of (A) preparing a first reactor having a content of xylene-soluble fraction at room temperature of 1 to 10% by weight and a melt flow rate (ASTM D- (B) a step of preparing a polybutene-1 polymer (a) in which the content of xylene-soluble fraction at room temperature is 10 < RTI ID = 0.0 > (B) having a melt flow rate (ASTM D-1238, temperature 190 占 폚, load of 2.16 kg) of 0.1 to 0.5 g / 10 min, and (C) Mixing 10 to 50% by weight of the polybutene-1 polymer (a) produced in the first reactor and 50 to 90% by weight of the polybutene-1 polymer (b) prepared in the second reactor.

The preparation of the polymers (a) and (b) is preferably carried out in a first reactor and a second reactor connected in parallel. This is because the polymers (a) and (b) have different stereoregularity and MFR, so that the polymers (a) and (b) are prepared in the first reactor and the second reactor separately.

The polymers (a) and (b) thus prepared can be prepared in a slurry state by physical mixing, i.e. stirring, in a mixer connected in series with each of the first reactor and the second reactor, in order to prepare the polybutene- have.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Example  One.

1, hydrogen, triethylaluminum as a cocatalyst and a silane compound as an electron donor were charged into a first reactor and a second reactor connected in parallel, and slurry polymerization was carried out at a reaction temperature of 80 ° C and a pressure of 17 bar, Polymers (a) and (b) having physical properties shown in Table 1 were prepared.

Then, 35% by weight of the polymer (a) and 65% by weight of the polymer (b) were put into a mixer connected in series with each of the first reactor and the second reactor, homogeneously mixed and then mixed with Tetrakis [methylene- 1 polymer composition of Example 1 was prepared by adding an anti-oxidant additive of Tris (2,4-di-tert-butylphenyl) .

Example  2 to 8 and Comparative Example  1 to 3

1 polymer composition of Examples 2 to 8 and Comparative Examples 1 to 3 was prepared in the same manner as in Example 1 except that the polymer (a) and the polymer (b) having physical properties shown in Tables 1 and 2 were used. .

division Properties unit Example  One  2  3  4  5 6 7 8 polymer
(a) MIE g / 10 min 3.2 2.1 1.8 2.5 4.6 2.5 2.2 4.4 MIP g / 10 min 16.9 10.1 9.4 11.3 23.5 12.1 10.8 22.4 Xylene
Melt weight% 2 One 3 One One 5 10 8 content weight% 35 40 40 30 20 50 38 47 polymer
(b) MIE g / 10 min 0.14 0.18 0.21 0.19 0.12 0.1 0.25 0.17 MIP g / 10 min 0.71 0.88 0.99 1.03 0.59 0.48 1.27 0.83 Xylene
Melt weight% 10 20 15 12 10 30 18 22 content weight% 65 60 60 70 80 50 62 53 Polybutene-1 polymer composition MIE g / 10 min 0.60 0.58 0.65 0.61 0.47 0.52 0.70 0.66 MIP g / 10 min 3.1 2.8 3.1 3.2 2.4 2.5 3.6 3.3 S / R (MIP / MIE) - 5.1 4.8 4.7 5.2 5.1 4.9 5.1 5.0 Xylene
Melt weight% 5 12 10 9 7 15 11 12

division Properties unit Comparative Example  One  2 3 polymer
(a) MIE g / 10 min 2.6 3.4 3.0 MIP g / 10 min 11.4 16.7 13.5 Xylene
Melt weight% 7 19 15 content weight% 40 30 35 polymer
(b) MIE g / 10 min 0.25 0.22 0.2 MIP g / 10 min 1.15 1.14 0.96 Xylene
Melt weight% 2 13 5 content weight% 60 70 65 Polybutene-1 polymer composition MIE g / 10 min 0.57 0.59 0.62 MIP g / 10 min 2.5 2.7 2.7 S / R (MIP / MIE) - 4.4 4.6 4.4 Xylene
Melt weight% 5 15 8

The physical properties of the polybutene-1 polymer (a), the polybutene-1 polymer (b) and the polybutene-1 polymer composition prepared in the above Examples and Comparative Examples were measured by the following methods.

Here, the physical properties of the polymer (a), the polymer (b) and the polybutene-1 polymer composition were measured by the same method as the content of the xylene-soluble fraction. Thus, the method of measuring the physical properties of the polymer (a) will be described below.

The xylene solubility fraction (xylene Melt )

In a glass flask equipped with a cooling device and a magnetic stirrer, 0.5 g of polybutene-1 polymer (a) and 50 ml of xylene were charged and the temperature was raised to the boiling point of the solvent for 30 minutes. The resulting solution was then kept under reflux and stirring for 30 minutes. The closed flask was maintained in an ice bath for 30 minutes and maintained in a constant temperature bath at 25 DEG C for an additional 30 minutes. The solid thus formed was filtered with a quick filtering paper, 100 mL of the filtered liquid was put into a pre-weighed aluminum container, and the container was heated on a heating plate under nitrogen flow to remove the solvent. The vessel was then held at 80 DEG C under vacuum until a constant weight was obtained. The residue was weighed and the weight percent of polymer (a) soluble in xylene at room temperature (25 캜) was calculated according to the following equation.

 XS (weight%) = (weight of residue / initial total weight of polybutene-1 polymer (a)) * amount of initial xylene

MIE ( Melt flow rate )

According to the method defined in ASTM D-1238, the polybutene-1 polymer (a) is measured under the conditions of a temperature of 190 ° C and a load of 2.16 kg, and the weight (g) of the polymer (a) Respectively.

MIP ( Melt flow rate )

According to the method defined in ASTM D-1238, the polybutene-1 polymer (a) is measured under the conditions of a temperature of 190 ° C under a load of 5 kg and expressed as the weight (g) of the polymer (a) .

Experimental Example

The physical properties of the compressed sheet prepared from the polybutene-1 polymer composition prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 3.

1. Surrender The tensile strength , Fracture The tensile strength , Fracture Tensile elongation

A polybutene-1 compression-molded sheet was prepared in accordance with the method defined in ISO 293 and processed according to the method specified in ISO 2817 to prepare a polybutene-1 test piece. The prepared test pieces were aged for 10 days in a desiccator at a temperature of 25 ° C and a humidity of 20%. Yield tensile strength, breaking tensile strength and elongation at break according to ISO 527 were measured using UTM manufactured by ZWICK.

2. Pipe formability and appearance

The polybutene-1 polymer composition prepared in the above Examples and Comparative Examples was molded in a pipe extruder at a molding speed of 18 m / min to produce a pipe. The appearance of the pipe thus prepared was visually observed, and evaluated based on the following criteria Respectively.

[Evaluation standard]

?: Excellent moldability of the pipe, no small rough uneven surface is formed on the inner and outer surfaces of the pipe, and excellent appearance of the pipe

Good: Moldability of the pipe was good, and a small rough rough tire was slightly formed on the inner and outer surfaces of the pipe,

?: Although the pipe can be formed, a large number of small and rough non-flat surfaces are formed on the inner and outer surfaces of the pipe,

×: Pipe can not be formed

division Example Comparative Example One 2 3 4 5 6 7 8 One 2 3 Yield Tensile Strength
(MPa) 19 17 18 19 17 17 19 18 20 14 16 Breaking tensile strength
(MPa) 33 34 33 31 32 33 34 34 30 30 37 Tensile elongation at break
(%) 280 297 290 287 282 302 298 301 277 313 319 Pipe Appearance ◎ ○ ○ ○ ○ ○ ◎ ○ △ △ △ Pipe formability ○ ○ ◎ ○ ◎ ○ ○ ○ ○ × △

As shown in Table 3, the polybutene-1 polymer compositions of Examples 1 to 8 containing two kinds of polybutene-1 polymers different in stereoregularity according to the present invention had tensile strength and elongation It was confirmed that it is excellent in strength, excellent in the formability and appearance of the pipe, and is suitable for the material of pipes for supplying hot water and water.

Claims (10)

(A) having a content of xylene-soluble fraction at room temperature of 1 to 10% by weight and a melt flow rate (ASTM D-1238, temperature 190 占 폚, load of 2.16 kg) of 1 to 5 g / Wow,
A polybutene-1 polymer (b) having a content of fraction soluble in xylene at room temperature of 10 to 30% by weight and a melt flow rate (ASTM D-1238, temperature 190 캜, load of 2.16 kg) of 0.1 to 0.5 g / ),
Wherein the polymer composition has a fractional content difference (DELTA) of 5 to 20 and a difference in melt flow rate (DELTA) of 1 to 5 in the polymer (a) and the polymer (b).
The polybutene-1 polymer composition according to claim 1, wherein the polymer composition is a mixture of 10 to 50% by weight of the polybutene-1 polymer (a) and 50 to 90% by weight of the polybutene- .
delete The polybutene-1 polymer composition according to claim 1, wherein the polymer composition satisfies the following formula (1) in a flow ratio (S / R) of 4.5 or more:

(Wherein MIP is the melt flow rate measured at ASTM D-1238, temperature 190 캜, load 5 kg, MIE is melt flow rate measured at ASTM D-1238, temperature 190 캜, load 2.16 kg).
The polybutene-1 polymer composition according to claim 1, wherein the polybutene-1 polymer (a) and the polybutene-1 polymer (b) are each independently a butene-1 polymer.
A molded article produced by molding the polybutene-1 polymer composition of any one of claims 1, 2, 4 and 5.
The formed article according to claim 6, wherein the molded article has a yield tensile strength of 17 to 19 MPa, a tensile strength at break of 31 to 34 MPa, and a tensile elongation at break of 280 to 297%.
The formed article according to claim 6, wherein the formed article is a pipe.
(A) 1 to 10% by weight of a fraction soluble in xylene at room temperature and 1 to 5 g / 10 min of a melt flow rate (ASTM D-1238, temperature 190 占 폚, load 2.16 kg) Preparing a polybutene-1 polymer (a)
(A) a second reactor having a content of xylene-soluble fraction at room temperature of 10 to 30% by weight and a melt flow rate (ASTM D-1238, temperature 190 캜, load of 2.16 kg) of 0.1 to 0.5 g / 10 min (B), wherein the polybutene-1 polymer
(C) 10 to 50% by weight of the polybutene-1 polymer (a) prepared in the first reactor and 50 to 90% by weight of the polybutene-1 polymer (b) prepared in the second reactor are mixed Comprising:
Wherein the polymer composition has a fractional content difference (DELTA) of the polymer (a) and the polymer (b) of 5 to 20 and a difference (DELTA) of the melt flow rate of 1 to 5 Gt;
10. The method of claim 9, wherein the mixer is connected in series with a first reactor and a second reactor, respectively.