KR101730723B1 - High melt flow polypropylene resin composition having improved high melt flow and mechanical properties - Google Patents
High melt flow polypropylene resin composition having improved high melt flow and mechanical properties Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
Abstract
Disclosed herein is a high dynamic impact block copolymer product having a melt index (MI) of 35 g / 10 min (230 캜, 2.16 kg load) or more which can be prepared using the Spherizone process without addition of peroxide. The present invention relates to an impact block copolymer comprising 0.01 to 0.5 parts by weight of a phosphorus-based antioxidant, 0.01 to 0.5 parts by weight of a phenol-based antioxidant, and 0.01 to 0.5 parts by weight of a phenol-based antioxidant based on 100 parts by weight of an impact block copolymer having a melt index (230.degree. C. under a load of 2.16 kg) 0.01 to 0.5 parts by weight of a polypropylene resin composition.
Description
The present invention relates to a polypropylene resin composition, and more particularly, to a high-molecular polypropylene resin composition having improved physical properties using a high-impact impact block copolymer.
Impact block copolymers are general-purpose olefin resins used in special situations requiring high impact resistance. They are used in a wide variety of applications, including food containers, automotive supplies, household goods, and industrial materials. Impact block copolymers are used in a variety of ways because they are less toxic than other plastics and have better physical properties such as low temperature impact strength than homo-polypropylene and good processability. Particularly, impact block copolymer having high flow rate is widely used for thin-walled containers and large injection molding because of good flowability.
A general impact block copolymer polymerization method is a method in which a catalyst and a propylene monomer are charged in a loop reactor to prepare a homo-polypropylene, and then an ethylene monomer is added in a gas phase reactor to form an amorphous ethylene-propylene copolymer, And an ethylene-propylene copolymer. The ethylene-propylene copolymer is in the form of an amorphous rubber and islands in the homo-polypropylene matrix. The absolute amount and type of dispersion of the ethylene-propylene copolymer affects the impact strength of the impact block copolymer.
On the other hand, in order to produce a high-impact block copolymer product having a melt index (MI) of 35 g / 10 min (230 ° C, 2.16 kg load) or more, a method of adding a peroxide (see Prior Art 1) (See the
[Prior Art]
- Prior Art 1: Korean Published Patent No. 10-2012-0051687 (2012.05.22)
- Prior Art 2: Korean Patent Publication No. 10-2014-0033225 (Apr. 17, 2014)
- Prior Art 3: Korean Patent Laid-Open No. 10-2009-0007044 (Jan. 16, 2009)
The present invention seeks to provide a high dynamic impact block copolymer product having a melt index (MI) of 35 g / 10 min (230 캜, 2.16 kg load) or more which can be prepared using the Spherizone process without addition of peroxide.
In one aspect of the present invention, there is provided an impact block copolymer composition comprising 0.01 to 0.5 parts by weight of a phosphorus-based antioxidant, 100 to 500 parts by weight of a phenol (meth) acrylate based on 100 parts by weight of an impact block copolymer having a melt index 0.01 to 0.5 parts by weight of an antioxidant and 0.01 to 0.5 parts by weight of a neutralizing agent.
Also, the impact block copolymer has an ethylene content of 4 to 12% by weight.
The present invention also provides a polypropylene resin composition characterized in that the phosphorus antioxidant is tris (2,4-di-t-butylphenyl) phosphite.
And the phenolic antioxidant is tetrakis [ethylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methadecene.
Also, the polypropylene resin composition is characterized in that the neutralizing agent is calcium stearate.
The polypropylene resin composition further comprises a nucleating agent.
In another aspect of the present invention, there is provided a molded article produced from the polypropylene resin composition.
Further, the molded article is an automobile part or a thin-walled injection molded article.
In the Spherizone process, production of impact block copolymers with high melt index of 35 g / 10 min or more was not possible without the addition of peroxide. However, the impact block copolymer used in the present invention is a high-dynamic impact block copolymer by controlling the pressure of the reactor and the amount of addition of hydrogen, and can realize a high melt viscosity of 35 g / 10 min or more without addition of peroxide.
Also, the impact block copolymer used in the present invention improves the mechanical properties by controlling the impact strength and viscosity of the high-impact block copolymer by increasing the absolute amount of the ethylene-propylene copolymer by controlling the amount of hydrogen and ethylene added in the gas phase reactor Thereby reducing color and odor.
In addition, when injection molding an automobile bumper or the like using a high-dynamic copper product containing peroxide, gas generation and flow mark are generated. However, since the product polymerized through the present invention has improved flowability, There is an effect that the flow mark generation and the flow mark problem are improved.
1 is a photograph showing a comparison of appearance of an automobile bumper injection-molded using the polypropylene resin composition produced according to Example 2 and Comparative Example 1,
2 is a graph showing the GC-MS (Gsa Chromatograph-Mass spectorophotometry) analysis results of the polypropylene resin composition prepared according to Example 2 and Comparative Example 1. Fig.
Hereinafter, the present invention will be described in detail with reference to preferred embodiments. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. It is to be understood that various equivalents and modifications may be substituted for those at the time of the present application.
The present inventors have found that it is impossible to manufacture high impact block copolymer products having a melt index (MI) of 35 g / 10 min (230 ° C, 2.16 kg load) or more without conventional peroxide addition in the manufacture of impact block copolymers using the Spherizone process As a result of studying the facts, it has been found that by controlling the pressure of the reactor and the amount of addition of hydrogen, it is possible to realize a high flowability of 35 g / 10 min or more as a high-dynamic impact block copolymer without addition of peroxide, It was.
Accordingly, the present invention provides a process for producing an impact block copolymer comprising 0.01 to 0.5 parts by weight of a phosphorus-based antioxidant, 0.01 to 0.5 parts by weight of a phenolic antioxidant based on 100 parts by weight of an impact block copolymer having a melt index (230 DEG C, 2.16 kg load) of 35 to 100 g / And 0.01 to 0.5 parts by weight of a neutralizing agent.
In the present invention, the impact block copolymer was produced through a Spherizone process. Unlike the conventional reactor, it was impossible to produce a high-impact block copolymer having a melt index of 35 g / 10 min or more without adding peroxide. However, It has been confirmed that by controlling the amount of pressure and hydrogen added, it is possible to produce a high impact impact block copolymer.
The impact block copolymer preparation through the Spherizone process is carried out in a gas phase polymerization process to polymerize homopolypropylene in an MZCR (Muti Zone Circulating Reaction) polymerization process and to produce an ethylene-propylene copolymer. The MZCR polymerization process consists of a single loop reactor, which limits the production of inherent homopropylene. Therefore, there is a drawback that an impact block copolymer having a melt index of 35 g / 10 min or more can not be produced. In the present invention, it is possible to produce an intrinsic impact block copolymer by elevating the pressure to improve this.
That is, in order to achieve high fluidity in the manufacture of an impact block copolymer using a Spherizone process, there is no known solution for controlling the pressure of the reactor and controlling the amount of hydrogen. However, in the present invention, It is possible to easily produce a high-dynamic impact block copolymer having a melt index of 35 g / 10 min or more by controlling the amount of hydrogen to be added to a specific range.
In order to produce a high-impact block copolymer having a melt index of 35 g / 10 min or more, the loop reactor pressure can be adjusted to 28 to 40 atm. To achieve a melt index of 65 g / 10 min or more, , And more preferably 33 atmospheric pressure, that is, 32 to 34 atmospheric pressure.
Thus, by controlling the reactor pressure in the Spherizone process, it is possible to easily produce the high-impact block copolymer by controlling the amount of hydrogenation in the polymerization reactor without adding peroxide.
On the other hand, the homogeneity of the homo-polypropylene of the loop reactor is increased by controlling the amount of hydrogenation in the reactor, and thus the impact strength tends to be lower than that of the product containing peroxide. In the present invention, the impact strength can be improved by increasing the ethylene-propylene copolymer by adjusting the amount of hydrogen and ethylene added in the gas reactor to improve the impact strength.
When the molecular weight of the ethylene-propylene copolymer is high, a flow mark may occur not only in the injection molding of an automobile part due to a high viscosity but also cause a gas mark to appear on the surface. However, the polymerized product according to the present invention can control the molecular weight of the ethylene-propylene copolymer, thereby improving gas generation and flow mark problems. In addition, yellowing phenomenon and odor problem in which the color of the injection molded article is changed to yellow by using no organic peroxide is improved.
Hereinafter, each constitution of the polypropylene resin composition according to the present invention will be described in more detail.
(1) Impact block copolymer
In the present invention, the impact block copolymer is prepared through a Spherizone reactor. For example, a propylene monomer is placed in a speriorion polymerization reactor, triethylaluminum, a phthalate catalyst, and a silane-based electron donor are introduced, vapor phase polymerization is carried out at a reaction temperature of 68 to 75 ° C and a predetermined atmospheric pressure to obtain an impact blocker Polymers can be produced, which can produce high-flow products by hydrogen.
The ethylene content of the impact block copolymer for high throughput implementation may be 4-12 wt%, preferably 8-12 wt%, more preferably 9-10 wt%. If the ethylene content is less than 4% by weight, the low temperature impact strength may be lowered. If the ethylene content is more than 12% by weight, the low temperature impact strength may be excellent, but the stiffness may be decreased.
The impact block copolymer resin may have a melt index of 35 to 100 g / 10 min (230 ° C, 2.16 kg load), preferably 60 to 100 g / 10 min. When the melt index is less than 35 g / 10 min, it can not be used as a thin film product or a high-flow product. When the melt index exceeds 100 g / 10 min, flow properties of the product increase but the polypropylene extrusion process condition must be changed. There is a disadvantage that it is fragile.
(2) Antioxidants
The polypropylene resin composition according to the present invention is required to simultaneously contain a phosphorus-based antioxidant and a phenol-based antioxidant as additives, wherein 0.01 to 0.5 parts by weight of the phosphorus-based antioxidant is added to 100 parts by weight of the impact block copolymer, Based antioxidant is 0.01 to 0.5 parts by weight. Preferably, 0.05 to 0.15 parts by weight of the phosphorus antioxidant and 0.05 to 0.2 parts by weight of the phenolic antioxidant may be included.
If the content of the phosphorus antioxidant is less than 0.01 part by weight, pyrolysis of the polypropylene resin itself may occur during processing, adversely affecting the physical properties. If the content is more than 0.5 parts by weight, the color change after molding may be affected.
When the content of the phenolic antioxidant is less than 0.01 part by weight, the physical properties such as the yield stress may be affected. When the amount of the phenolic antioxidant is more than 0.5 parts by weight, Can affect the color change.
The phosphorus-based antioxidant and the phenol-based antioxidant are not particularly limited, and they may be used alone or in combination of two or more thereof. However, in view of maintaining an optimum level of low-temperature impact strength and flexural modulus, the phosphorus antioxidant is tris (2,4-di-t-butylphenyl) phosphite, the phenolic antioxidant is tetrakis [ Di-t-butyl-4-hydroxyphenyl) propionate] methane.
(3) Neutralizer
In order to neutralize the residual catalyst in the polypropylene resin, the polypropylene resin composition according to the present invention may contain 0.01 to 0.5 parts by weight, preferably 0.05 to 0.2 parts by weight, of a neutralizing agent based on 100 parts by weight of the impact block copolymer.
Examples of the neutralizing agent include fatty acid metal salts such as lithium stearate, calcium stearate and sodium stearate, and fatty acid amides such as ethylenebisstearoamide and stearic acid amide. However, It is preferable to use calcium stearate in view of the above.
In addition, the present invention may further include a nucleating agent to prevent a decrease in rigidity and a decrease in heat resistance due to a decrease in a heat distortion temperature due to a decrease in flexural modulus. The nucleating agent may be added in an amount of 0.05 to 1 part by weight, preferably 0.1 to 0.3 part by weight based on 100 parts by weight of the impact block copolymer. When the content of the nucleating agent is less than 0.05 part by weight, it is difficult to obtain a sufficient flexural modulus and the crystallization rate effect may be deteriorated. When the amount of the nucleating agent is more than 1 part by weight, low temperature impact strength is lowered and further property improvement in terms of flexural modulus and crystallization speed is expected It can be difficult.
As such a nucleus agent, organic nucleating agents such as zinc and calcium salt compounds, sorbitol compounds, phosphoric acid ester compounds and the like and inorganic nucleating agents such as talc can be used, but the remarkable improvement in rigidity and the rate of crystallization are further shortened, It is most preferable to use zinc and calcium salt compounds in order to maintain an optimum level of zinc and calcium salts.
In addition, the low-temperature impact strength and flexural modulus of the polypropylene resin composition to which the antistatic agent, the anti-blocking agent, the slip agent, the weathering / light stabilizer, the pigment, It can be added within a range that does not deteriorate.
The molded article manufactured using the high dynamic impact block copolymer according to the present invention has excellent stiffness and IZOD impact strength and can be used for a thin film container for various applications. It can also be used effectively as an automotive component material.
Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. However, the following examples are illustrative of the present invention, and the present invention is not limited to the examples described below.
Example 1
A propylene monomer was placed in a speri zone polymerization reactor, and triethylaluminum, a phthalate catalyst, and a silane-based electron donor were introduced, and vapor phase polymerization was carried out at a reaction temperature of 68 to 75 ° C and a pressure of 30 to 33 atm to obtain an ethylene copolymer having an ethylene content of 8.5 to 9.5 wt% Impact Block Copolymer was prepared, and a product with a melt index of 55-65 g / 10 min was produced by hydrogen.
Thereafter, 0.15 part by weight of a phosphorus antioxidant (tris (2,4-di-t-butylphenyl) phosphite, Songwon Industry), 0.15 part by weight of a phenolic antioxidant (tetrakis 0.1 part by weight of a polyoxyethylene /? - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, Songwon Industry) and 0.1 part by weight of a neutralizing agent (calcium stearate, Minute, followed by extrusion with a twin-screw extruder at 180 to 220 ° C to obtain a pellet-shaped polypropylene resin composition. The melt index is in the range of 55 to 65 g / 10 min.
Example 2
A propylene monomer is added to a polymerization reactor of a speriorion, and triethylaluminum, a phthalate catalyst, and a silane-based electron donor are introduced, and gas phase polymerization is carried out at a reaction temperature of 68 to 75 ° C and a pressure of 30 to 33 atm to give an ethylene content of 9 to 10% Impact Block Copolymer was prepared, and a product with a melt index of 55-65 g / 10 min was produced by hydrogen.
0.15 part by weight of a phosphorus antioxidant (tris (2,4-di-t-butylphenyl) phosphite, Songwon Industry), 0.15 part by weight of a phenolic antioxidant (tetrakis [ethylene- 0.1 part by weight of a neutralizing agent (calcium stearate, manufactured by Songwon Industrial Co., Ltd.) and 0.1 parts by weight of a neutralizing agent were mixed in a Henschel mixer for 5 minutes And then extruded by a twin-screw extruder at 180 to 220 ° C to obtain a pellet-shaped polypropylene resin composition. The melt index is in the range of 55 to 65 g / 10 min.
Example 3
A propylene monomer was placed in a speri zone polymerization reactor, and triethylaluminum, a phthalate catalyst, and a silane-based electron donor were introduced, and vapor phase polymerization was carried out at a reaction temperature of 68 to 75 ° C and a pressure of 30 to 33 atm to obtain an ethylene copolymer having an ethylene content of 8.5 to 9.5 wt% Impact block copolymer was prepared and the product was produced by hydrogen with a melt index of 75-85 g / 10 min.
0.15 part by weight of a phosphorus antioxidant (tris (2,4-di-t-butylphenyl) phosphite, Songwon Industry), 0.15 part by weight of a phenolic antioxidant (tetrakis [ethylene- 0.1 part by weight of a neutralizing agent (calcium stearate, manufactured by Songwon Industrial Co., Ltd.) and 0.1 parts by weight of a neutralizing agent were mixed in a Henschel mixer for 5 minutes And then extruded by a twin-screw extruder at 180 to 220 ° C to obtain a pellet-shaped polypropylene resin composition. The melt index is in the range of 75 to 85 g / 10 min.
Comparative Example 1
A propylene monomer was placed in a speri zone polymerization reactor, and triethylaluminum, a phthalate catalyst, and a silane-based electron donor were introduced, and vapor phase polymerization was carried out at a reaction temperature of 68 to 75 ° C and a pressure of 28 atm to give an impact having an ethylene content of 7.5 to 8.5 wt% Block copolymers were prepared and hydrogen was used to produce products with a melt index of 35-45 g / 10 min.
Thereafter, 0.02 to 0.03 part by weight of an organic peroxide (diisobutyl peroxide), 0.1 part by weight of a phosphorus antioxidant (tris (2,4-di-t-butylphenyl) phosphite, , 0.1 part by weight of a phenolic antioxidant (0.1 part by weight of tetrakis [ethylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight of calcium carbonate, manufactured by Songwon Industrial Co., Ltd.) was mixed with a Henschel mixer for 5 minutes, and extruded by a twin-screw extruder at 180 to 220 ° C to obtain a pelletized polypropylene resin composition. The melt index is in the range of 55 to 65 g / 10 min.
Comparative Example 2
A propylene monomer was placed in a speri zone polymerization reactor, and triethylaluminum, a phthalate catalyst, and a silane-based electron donor were introduced, and vapor phase polymerization was carried out at a reaction temperature of 68 to 75 ° C and a pressure of 28 atm to give an impact having an ethylene content of 7.5 to 8.5 wt% Block copolymers were prepared and hydrogen was used to produce products with a melt index of 35-45 g / 10 min.
Thereafter, 0.03 to 0.04 part by weight of an organic peroxide (diisobutyl peroxide), 0.05 part by weight of a phosphorus antioxidant (tris (2,4-di-t-butylphenyl) phosphite, , 0.1 part by weight of a phenolic antioxidant (0.1 part by weight of tetrakis [ethylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight of calcium carbonate, manufactured by Songwon Industrial Co., Ltd.) was mixed with a Henschel mixer for 5 minutes, and extruded by a twin-screw extruder at 180 to 220 ° C to obtain a pelletized polypropylene resin composition. The melt index is in the range of 75 to 85 g / 10 min.
Experimental Example One
The pellet-shaped polypropylene resin compositions prepared according to the above Examples and Comparative Examples were injected with a molding extruder (Lotte Chemical Co., Ltd.) to prepare specimens for measuring properties. The physical properties of each of the prepared specimens were measured by the following methods, and the results of the measurement are shown in Table 1 below.
[Measurement of physical properties]
1) Melt index: measured according to ASTM evaluation method D1238 at 230 占 폚 under a load of 2.16 kg.
2) Ethylene-Propylene Copolymer Content: The sample was extracted with xylene.
3) Ethylene-propylene copolymer viscosity: The ethylene-propylene copolymer obtained using the xylene was analyzed by GPC.
4) Flexural modulus: According to ASTM evaluation method D790, ASTM injection specimens were measured at 23 ° C and 50% relative humidity.
5) IZOD Impact Strength: Notched injection specimens were measured at 23 ° C and 50% relative humidity according to ASTM Rating Method D256.
6) Yellow index: A 2 mm thick injection specimen made of ASTM mold was analyzed using a color meter.
7) Volatile Matter (VM): Volatile matter generated at 90 ° C for 2 hours was measured
Comparative Examples 1 and 2 are products in which an organic peroxide is added to produce an impact block copolymer having a melt index of 60 to 80 g / 10 min. Examples 1 to 3 are impact block copolymers produced without using organic peroxides. At this time, in Comparative Examples 1 and 2, the pressure of the reactor was 28 atmospheres, and Examples 1 and 3 were relatively higher at 33 atmospheres. This means that the reactor pressure must be increased from 28 atmospheres to 33 atmospheres in order to produce a high-dynamic impact block copolymer with a melt index of 60-100 g / 10 min in a Spherizon reactor without the addition of organic peroxide. It is also possible to increase the melt index of the homo-polypropylene of the loop reactor in order to produce a high-impact block copolymer without adding organic peroxides. In this case, the impact strength tends to be lower than that of the product to which the peroxide is added. The content of ethylene-propylene serves as an amorphous rubber of the impact block copolymer and is an important criterion for determining the impact strength. Therefore, in the present invention, the ethylene content of the gas phase reactor is controlled to control the content of ethylene-propylene. In Examples 1 to 3 according to the present invention, the ethylene content of Comparative Examples 1 and 2 was increased to 9.0 to 9.5% by weight, which is higher than the ethylene content of 8.0% by weight. As the ethylene content is increased, the ethylene-propylene content is increased and the IZOD impact strength is increased.
Experimental Example 2
In order to confirm the flowability of the examples and comparative examples, the injection molding was carried out by a company that manufactures automobile bumpers using the polypropylene resin composition prepared according to Example 2 and Comparative Example 1. 60 to 70 parts by weight of an impact block copolymer composition, 10 to 20 parts by weight of rubber and 10 to 20 parts by weight of talc are mixed for 5 minutes in a Henschel mixer as a raw material used in an automobile bumper injection molding, A pellet-like composition obtained by extruding by a twin-screw extruder was used.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing the appearance of an automobile bumper injection molded using the polypropylene resin composition produced according to Example 2 and Comparative Example 1. FIG.
Referring to FIG. 1 and Table 1, the surface flowability of the injection molded automobile bumper using the polypropylene resin composition prepared according to Example 2 and Comparative Example 1 can be confirmed. That is, as can be seen from the results of Table 1, the ethylene-propylene viscosity decreased from 4.45 to 4.15 in Example 2 in which no organic peroxide was added, as compared with Comparative Example 1 in which organic peroxide was added. The decrease in ethylene-propylene viscosity means that even impact block copolymers having the same melt index have better flow and moldability. In FIG. 1, in the case of Comparative Example 1, a flow mark is generated due to low fluidity, whereas in Example 1, the flow mark is improved.
Experimental Example 3
Volatile matter (VM) was measured for Example 2 and Comparative Example 1 in order to confirm the degree of off-setting according to presence or absence of organic peroxide, and the results of the experiment are shown in Table 1 above. VM is a measurement of the volatile matter produced by carbonizing the impact block copolymer. A high VM means that there are many volatile components and bad odors.
Referring to Table 1, it can be seen that the VM content of Examples 1 to 3 in which no organic peroxide was added was decreased from 1.25 to 1.55% by weight to 0.42 to 0.43% by weight, compared with Comparative Examples 1 and 2 in which organic peroxide was added .
In addition, GC-MS (Gsa Chromatograph-Mass spectorophotometry) analysis was performed to identify the cause of the odor. The headspace adjustment tool of the GC-MS was used, and the gas generated at 200 ° C for 20 minutes was analyzed. The analysis result is shown in FIG.
2, most of the volatile components generated in Comparative Example 1 are low-molecular organic compounds of 4-methylheptane and 2,4-dimethyl-1-heptane, and t-butanol, 2,2- -2-butanol-based alcohols were the most abundant. On the other hand, in Example 2 in which no organic peroxide was added, a small amount of low molecular organic material was detected. It can be seen that the odor generated in Comparative Example 1 is generated due to the alcohol-based material generated by the reaction of the unreacted organic peroxide with the impact block copolymer. As a result, it can be seen that when the organic peroxides are not added to Comparative Examples 1 to 3, they are selected as a molding material, it is possible to improve the problem of bad odor.
In order to confirm the yellowing problem of the impact block copolymer due to the addition of the organic peroxide, the yellow index for the examples and comparative examples was measured and the results are shown in Table 1 above. A high yellowing index means that the color of the measurement sample changes to yellow. Referring to Table 1, it can be seen that the yellowing index of Examples 1 to 3 in which no organic peroxide was added was lowered from -4.59 to -4.92 to -6.70 to -7.22 as compared with Comparative Examples 1 and 2 in which organic peroxide was added. This indicates that the organic peroxide reacted and changed to yellow.
Thus, according to the present invention, it is possible to produce a high dynamic impact copolymer using a Spherizone reactor without adding an organic peroxide, thereby solving the problem of flow mark, odor and yellowing.
While the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, Such modifications and changes are to be considered as falling within the scope of the following claims.
Claims (8)
Mixing and extruding 0.01 to 0.5 parts by weight of a phosphorus antioxidant, 0.01 to 0.5 parts by weight of a phenol antioxidant, and 0.01 to 0.5 parts by weight of a neutralizer with respect to 100 parts by weight of the impact block copolymer;
By weight based on the total weight of the polypropylene resin composition.
Wherein the impact block copolymer has an ethylene content of 4 to 12 wt%.
Wherein the phosphorus antioxidant is tris (2,4-di-t-butylphenyl) phosphite.
Wherein the phenolic antioxidant is tetrakis [ethylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methadecane.
Wherein the neutralizing agent is calcium stearate.
Wherein the polypropylene resin composition further comprises a nucleating agent.
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