CN114907643A - Polypropylene composition, polypropylene material, preparation method and application thereof - Google Patents
Polypropylene composition, polypropylene material, preparation method and application thereof Download PDFInfo
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- CN114907643A CN114907643A CN202110184320.7A CN202110184320A CN114907643A CN 114907643 A CN114907643 A CN 114907643A CN 202110184320 A CN202110184320 A CN 202110184320A CN 114907643 A CN114907643 A CN 114907643A
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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
- C08L23/12—Polypropene
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to the technical field of polypropylene material preparation, and discloses a polypropylene composition, a polypropylene material, a preparation method and application thereof, wherein the polypropylene composition contains homopolymerized polypropylene, a thermoplastic elastomer, a nucleating agent and an antioxidant, and based on the total weight of the polypropylene composition, the content of the homopolymerized polypropylene is 50-95 wt%, the content of the thermoplastic elastomer is 4-50 wt%, the content of the nucleating agent is 0.05-0.5 wt%, and the content of the antioxidant is 0.05-1 wt%; wherein the thermoplastic elastomer is selected from at least one of styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, polyolefin elastomer, thermoplastic polyamide, thermoplastic polyurethane and thermoplastic polyester. The polypropylene material prepared from the polypropylene composition has high toughness, high heat resistance, low haze and high fluidity, can be sterilized at high temperature and high pressure, and is suitable for prefilled syringe injectors.
Description
Technical Field
The invention relates to the technical field of polypropylene material preparation, in particular to a polypropylene composition, a polypropylene material prepared from the polypropylene composition, a preparation method of the polypropylene material, and application of the polypropylene composition and/or the polypropylene material in a prefilled syringe.
Background
With the gradual increase of high-temperature and high-pressure sterilization modes, the requirements of medical new materials on the high-temperature resistance of products are higher and higher, and various injection molding products need to be treated in a long-time steam sterilization mode to meet the requirements of medical sanitation. The pre-filled type washing pipe injector is mainly prepared from polypropylene materials, but the common polypropylene cannot have the performances of high temperature resistance, high pressure resistance and high toughness.
Disclosure of Invention
The invention aims to solve the problem that polypropylene in the prior art cannot have high temperature resistance, high pressure resistance and high toughness, and provides a polypropylene composition, a polypropylene material, and a preparation method and application thereof.
In order to achieve the above object, the first aspect of the present invention provides a polypropylene composition comprising homo-polypropylene, a thermoplastic elastomer, a nucleating agent and an antioxidant, wherein the homo-polypropylene is contained in an amount of 50 to 95 wt%, the thermoplastic elastomer is contained in an amount of 4 to 50 wt%, the nucleating agent is contained in an amount of 0.05 to 0.5 wt%, and the antioxidant is contained in an amount of 0.05 to 1 wt%, based on the total weight of the polypropylene composition;
wherein the thermoplastic elastomer is selected from at least one of styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, polyolefin elastomer, thermoplastic polyamide, thermoplastic polyurethane and thermoplastic polyester.
In a second aspect, the present invention provides a polypropylene material prepared by melt blending and extrusion granulation of the polypropylene composition as described above.
In a third aspect of the present invention, a method for preparing a polypropylene material is provided, which comprises melt blending homo-polypropylene, a thermoplastic elastomer, a nucleating agent and an antioxidant, and extruding for granulation.
The invention provides the application of the polypropylene material in the prefilled type wash pipe injector.
By the technical scheme, the polypropylene material prepared from the polypropylene composition has the characteristics of good toughness, high heat resistance, low haze, good fluidity and high-temperature and high-pressure sterilization, and can be used for preparing a prefilled syringe injector.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a polypropylene composition, which comprises homopolymerized polypropylene, thermoplastic elastomer, nucleating agent and antioxidant, wherein based on the total weight of the polypropylene composition, the content of the homopolymerized polypropylene is 50-95 wt%, the content of the thermoplastic elastomer is 4-50 wt%, the content of the nucleating agent is 0.05-0.5 wt%, and the content of the antioxidant is 0.05-1 wt%;
wherein the thermoplastic elastomer is selected from at least one of styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, polyolefin elastomer, thermoplastic polyamide, thermoplastic polyurethane and thermoplastic polyester.
In some embodiments of the present invention, the homopolypropylene may be present in an amount of 50 to 95 wt%, specifically, for example, 50 wt%, 55 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 95 wt%, or any number in a range of any two of these values, based on the total weight of the polypropylene composition. In order to increase the heat resistance of the polypropylene material, the homopolypropylene is preferably contained in an amount of 65 to 95% by weight, more preferably 75 to 95% by weight. In the case where the content of the homo-polypropylene is less than 50% by weight, the heat resistance of the resulting polypropylene material will be insufficient; in case that the content of the homo-polypropylene is higher than 95 wt%, the toughness of the prepared polypropylene material will be insufficient.
In some embodiments of the present invention, in order to increase the heat resistance of the polypropylene material, it is preferable that the load deformation temperature of the homo-polypropylene is 85 ℃.
In some embodiments of the present invention, preferably, the melt mass flow rate of the homo-polypropylene under a 2.16kg load at 230 ℃ is 1-30g/10 min; more preferably, the melt mass flow rate of the homo-polypropylene is 5-25g/10min at 230 ℃ under a load of 2.16 kg; further preferably, the melt mass flow rate of the homopolymerized polypropylene is 8-20g/10min at 230 ℃ under the action of 2.16kg load. The homo-polypropylene with the melt mass flow rate can have excellent mechanical strength and fluidity.
In some embodiments of the invention, the melt mass flow rate is determined with reference to GB/T3682, wherein the test conditions include: the temperature was 230 ℃ and the load was 2.16 kg.
In some embodiments of the present invention, the homopolypropylene may be obtained by commercially available methods or by various methods known to those skilled in the art, and will not be described herein.
In some embodiments of the present invention, the thermoplastic elastomer can be present in an amount of 4 to 50 wt%, specifically, for example, 4 wt%, 15 wt%, 25 wt%, 30 wt%, 35 wt%, 45 wt%, 50 wt%, or any number in the range of any two of these values, based on the total weight of the polypropylene composition. In order to increase the toughness of the polypropylene material, the thermoplastic elastomer is preferably present in an amount of 4 to 35 wt.%, more preferably 4 to 25 wt.%. In the case where the content of the thermoplastic elastomer is less than 4% by weight, the toughness of the prepared polypropylene material will be insufficient; in the case where the content of the thermoplastic elastomer is more than 50% by weight, the heat resistance of the resulting polypropylene material will be insufficient.
In some embodiments of the present invention, in order to increase the toughness of the polypropylene material, the Shore hardness of the thermoplastic elastomer is preferably less than or equal to 90A, and more preferably less than or equal to 70A.
In some embodiments of the present invention, the thermoplastic elastomer is selected from at least one of styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, polyolefin elastomer, thermoplastic polyamide, thermoplastic polyurethane and thermoplastic polyester, and preferably, the thermoplastic elastomer is selected from polyolefin elastomer and/or hydrogenated styrene-butadiene-styrene block copolymer in order to increase the toughness of the polypropylene material.
In some embodiments of the present invention, in order to increase the toughness of the polypropylene material, it is preferable that the content of styrene in the hydrogenated styrene-butadiene-styrene block copolymer is 5 to 25% by weight, more preferably 8 to 20% by weight, and still more preferably 8 to 15% by weight.
In some embodiments of the present invention, the nucleating agent may be present in an amount of 0.05 to 0.5 wt%, specifically, for example, 0.05 wt%, 0.08 wt%, 0.1 wt%, 0.15 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, and any number in the range of any two of these values, based on the total weight of the polypropylene composition. In order to increase the heat resistance and reduce the haze of the polypropylene material, the nucleating agent is preferably contained in an amount of 0.05 to 0.3 wt%, more preferably 0.1 to 0.3 wt%. In the case where the content of the nucleating agent is less than 0.05% by weight, the heat resistance of the resulting polypropylene material will be insufficient; in case that the content of the nucleating agent is more than 0.5 wt%, the toughness of the prepared polypropylene material will be insufficient.
In some embodiments of the present invention, the nucleating agent may be at least one selected from the group consisting of metal phosphate-based organic nucleating agents, metal carboxylate-based organic nucleating agents, and sorbitol derivatives.
The metal phosphate-based organic nucleating agent of the present invention is not particularly limited, and for example, the metal phosphate-based organic nucleating agent may be at least one selected from the group consisting of sodium 2,2' -methylenebis (4, 6-di-t-butylphenyl) phosphate, lithium 2,2' -methylenebis (4, 6-di-t-butylphenyl) phosphate, potassium 2,2' -methylenebis (4, 6-di-t-butylphenyl) phosphate, magnesium 2,2' -methylenebis (4, 6-di-t-butylphenyl) phosphate and aluminum 2,2' -methylenebis (4, 6-di-t-butylphenyl) phosphate, preferably sodium 2,2' -methylenebis (4, 6-di-t-butylphenyl) phosphate, lithium 2,2' -methylenebis (4, 6-di-t-butylphenyl) phosphate and 2, at least one of aluminum 2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate.
The metal carboxylate organic nucleating agent is not particularly limited in the present invention, and for example, the metal carboxylate organic nucleating agent may be selected from at least one of sodium succinate, sodium 4-methylpentanoate, adipic acid, sodium glutarate, sodium caproate, aluminum adipate, tert-butyl aluminum benzoate, potassium benzoate, lithium benzoate, sodium cinnamate, and sodium β -napthoate, and preferably at least one of aluminum benzoate, potassium benzoate, and lithium benzoate.
The sorbitol derivative of the present invention is not particularly limited, and for example, the sorbitol derivative may be at least one selected from the group consisting of 1,3,2, 4-dibenzylidene sorbitol, 1,3,2, 4-bis (p-methyldibenzylidene) sorbitol, 1,3,2, 4-bis (3, 4-dimethyldibenzylidene) sorbitol, 1,3,2, 4-bis (4-methyldibenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, bis (p-methylbenzylidene) sorbic acid, bis- (p-ethyldibenzylidene isopropyl) sorbitol, bis (p-chloro-substituted benzylidene) sorbitol, bis (p-chloromethyldibenzylidene) sorbitol, 4' - (dimethylthiodibenzylidene) sorbitol and 1-propyl-1, 3,2,4, -bis (p-n-propyldibenzylidene) sorbitol, preferably at least one of 1,3,2, 4-dibenzylidene sorbitol, 1,3,2, 4-bis (p-methyldibenzylidene) sorbitol and 1,3,2, 4-bis (3, 4-dimethyldibenzylidene) sorbitol.
In some embodiments of the present invention, preferably, the nucleating agent is selected from at least one of sodium 2,2 '-methylenebis (4, 6-di-tert-butylphenyl) phosphate, aluminum 2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate and 1,3,2, 4-bis (3, 4-dimethyldibenzylidene) sorbitol.
In some embodiments of the present invention, in order to improve the high temperature and high pressure sterilization processing bearing capacity of the polypropylene material, the purity of the nucleating agent is preferably greater than or equal to 90%.
In some embodiments of the present invention, the antioxidant may be present in an amount of 0.05 to 1 wt%, specifically, for example, 0.05 wt%, 0.15 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, or any number in the range of any two of these values, based on the total weight of the polypropylene composition. In order to increase the aging resistance of the polypropylene material, the antioxidant is preferably contained in an amount of 0.05 to 0.5 wt%, more preferably 0.05 to 0.3 wt%. In the case that the content of the antioxidant is less than 0.05 wt%, the prepared polypropylene material has insufficient oxidation resistance; in the case where the content of the antioxidant is more than 1% by weight, it is liable to be precipitated after high-temperature and high-pressure sterilization.
In some embodiments of the present invention, the antioxidant can be any of various known materials capable of preventing or retarding aging of the polypropylene composition, for example, phenolic antioxidants and/or phosphite antioxidants.
The kind of the phenolic antioxidant is not particularly limited in the present invention, and for example, the phenolic antioxidant may be at least one selected from the group consisting of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (also referred to as antioxidant 1010), n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (also referred to as antioxidant 1076), 2, 6-di-tert-butyl-4-methylphenol (also referred to as antioxidant 264), 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (also referred to as antioxidant 330) and 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (also referred to as antioxidant 3114), preferably at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 2, 6-tertiary butyl-4-methylphenol, more preferably pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and particularly preferably pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
The kind of the phosphite antioxidant is not particularly limited in the present invention, for example, the phosphite antioxidant may be selected from at least one of tris (2, 4-di-t-butylphenyl) phosphite (also referred to as antioxidant 168), (nonylphenyl) phosphite (also referred to as antioxidant TNP), dioctadecyl pentaerythritol diphosphite (also referred to as antioxidant 618) and bis (2, 4-di-t-butylphenol) pentaerythritol diphosphite (also referred to as antioxidant 626), preferably at least one of tris (2, 4-di-t-butylphenyl) phosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite and dioctadecyl pentaerythritol diphosphite, more preferably tris (2, 4-di-t-butylphenyl) phosphite and/or bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite is particularly preferred.
In some embodiments of the present invention, in order to increase the aging resistance of the polypropylene material, it is preferable that the antioxidant comprises pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butylphenyl) phosphite in a weight ratio of 1: 1-2.
According to a particularly preferred embodiment of the present invention, in the polypropylene composition, when the melt mass flow rate of the homo-polypropylene under the action of a 2.16kg load at 230 ℃ is 8-20g/10min, the load deformation temperature is more than or equal to 85 ℃; the thermoplastic elastomer is selected from polyolefin elastomer and/or hydrogenated styrene-butadiene-styrene block copolymer, the content of styrene in the hydrogenated styrene-butadiene-styrene block copolymer is 8-15 wt%, and the Shore hardness of the thermoplastic elastomer is less than or equal to 70A; the nucleating agent is selected from at least one of 2,2 '-methylene bis (4, 6-di-tert-butylphenyl) sodium phosphate, 2' -methylene bis (4, 6-di-tert-butylphenyl) aluminum phosphate and 1,3,2, 4-bis (3, 4-dimethylbenzylidene) sorbitol, and the purity thereof is not less than 90%; the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris (2, 4-di-tert-butylphenyl) phosphite, and the weight ratio of the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester to the tris (2, 4-di-tert-butylphenyl) phosphite is 1: 1-2, the heat resistance, toughness, transparency and fluidity of the polypropylene material can be particularly improved, and the polypropylene material is very beneficial to high-temperature high-pressure sterilization and processing.
The second aspect of the present invention provides a polypropylene material, wherein the polypropylene material is prepared by melt blending and extrusion granulation of a polypropylene composition. The kinds and amounts of the components in the polypropylene composition can be reasonably selected according to the above description, and will not be described herein again.
The third aspect of the invention provides a method for preparing a polypropylene material, which comprises the steps of carrying out melt blending and extrusion granulation on homo-polypropylene, a thermoplastic elastomer, a nucleating agent and an antioxidant, and specifically comprises the following steps: firstly, the homopolymerized polypropylene, the thermoplastic elastomer, the nucleating agent and the antioxidant are melted and blended, and then the mixture is extruded and granulated in a granulator. The types and the amounts of the homo-polypropylene, the thermoplastic elastomer, the nucleating agent and the antioxidant can be reasonably selected according to the above description, and will not be described herein again.
In some embodiments of the present invention, the equipment and conditions for melt blending are not particularly limited, as long as the components of the composition are uniformly mixed, and for example, a high-speed mixer can be used for melt blending, the rotation speed of the mixer can be 800-1000rpm, the blending temperature can be room temperature, and the blending time can be 1-10 min.
In some embodiments of the present invention, the equipment and conditions for the extrusion granulation are not particularly limited as long as the components in the composition can be sufficiently mixed and melted, for example, the equipment for the extrusion granulation is a twin-screw extruder, the rotation speed of the extruder can be 150-200rpm, and the extrusion temperature can be 170-230 ℃.
In a fourth aspect, the present invention provides a use of a polypropylene material in a prefilled syringe.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
In the following examples and comparative examples, unless otherwise specified, the compounds, reagents and the like used are commercially available, in which:
the homo-polypropylene resin is purchased from Yanshan petrochemical company, the mark is K1118, and the melt mass flow rate is 18g/10 min;
hydrogenated styrene-butadiene-styrene block copolymer (SEBS) was purchased from Yueyang petrochemical company under the designation YH506, wherein Shore hardness was 55A and styrene content was 11% by weight;
the polyolefin elastomer is purchased from ExxonMobil and has the mark 6202, wherein the Shore hardness is 65A, and the ethylene content is 15 weight percent;
2,2' -methylenebis (4, 6-di-tert-butylphenyl) aluminum phosphate is purchased from Shenzhen Huixin plastics chemical Co., Ltd, and the brand is NA-21, and the purity is 95%;
sodium 2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate is available from Ware corporation under the designation NAP-50, with a purity of 95%;
1,3,2, 4-bis (3, 4-dimethyldibenzylidene) sorbitol is available from Melenken under the designation 3988 with a purity of 95%;
pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) was purchased from Shijiazhuang Jiatuo Kangtu chemical science and technology Co., Ltd., brand 1010;
the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (antioxidant 1076) is purchased from Shijiazhuang Jiatuo chemical technology Co., Ltd, and is marked by 1076;
tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168) was obtained from Shijiazhuang Jiatuo chemical science and technology Co., Ltd under the brand number 168;
bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (antioxidant 626) was obtained from Shijiazhuang Seiko chemical technology Ltd under model/brand 626.
The test methods referred to in the following examples and comparative examples are as follows:
(1) the melt mass flow rate was tested with reference to GB/T3682-2000, and the test conditions included: the temperature is 230 ℃, and the load is 2.16 kg;
(2) the impact strength of the simply supported beam notch is tested according to GB/T1043.1-2008, and the test conditions comprise: the temperature is 23 ℃;
(3) the load deformation temperature is tested according to ISO 75-2: 2013;
(4) the haze is tested according to GB/T2410-2008;
(5) the sterilization property can be tested according to the change of haze before and after autoclaving, and the sterilization conditions include: the temperature is 110 deg.C, the pressure is 0.2MPa, and the time is 30 min.
(6) The oxidative induction period was tested with reference to GB/T17391-1998 under the following test conditions: the temperature was 200 ℃.
Example 1
Mixing the homopolymerized polypropylene, the thermoplastic elastomer, the nucleating agent and the antioxidant in a high-speed mixer at the temperature of 25 ℃ and the rotating speed of 800rpm for 10min to obtain a mixture; then adding the mixture into a double-screw extruder, and carrying out coupling extrusion granulation to obtain the polypropylene material, wherein the process conditions of the double-screw extruder comprise: the extrusion temperature was 200 ℃ and the extruder speed was 180 rpm.
Wherein the kinds and amounts of the raw materials in the polypropylene composition are shown in Table 1 based on the total weight of the polypropylene composition.
Examples 2 to 10
A polypropylene material was prepared by following the procedure of example 1, except for the kinds and amounts of the respective raw materials in the polypropylene composition, as specifically shown in Table 1.
TABLE 1 kinds and amounts of raw materials in the polypropylene compositions of examples
Example 11
The procedure of example 1 was followed except that "K1118" was replaced with "K1118-GD available from Yanghua having a melt mass flow rate of 35g/10min at 230 ℃ under a 2.16kg load and a load deformation temperature of 82 ℃".
Example 12
The method of example 1 was followed except that "YH 506" was replaced with "YH 502 available from Yueyang petrochemical company, wherein Shore hardness was 95A and styrene content was 30 wt%".
Example 13
The procedure of example 1 was followed except that "NAP-50" was replaced with "NAP-50-1 purchased from Nuclear Co., Ltd., 85% purity".
Example 14
The procedure of example 1 was followed, except that "0.1 parts by weight of the antioxidant 168" was replaced with "0.05 parts by weight of the antioxidant 168".
Comparative example 1
The procedure of example 1 was followed except that "90 parts by weight of K1118" was replaced with "98 parts by weight of K1118".
Comparative example 2
The procedure of example 1 was followed except "9.7 parts by weight YH 506" was replaced with "3 parts by weight YH 506".
Comparative example 3
The procedure of example 1 was followed, except that "0.15 part by weight of NAP-50" was replaced with "0.02 part by weight of NAP-50".
Comparative example 4
The procedure of example 1 was followed except that "0.05 parts by weight of the antioxidant 1010 and 0.1 parts by weight of the antioxidant 168" was replaced with "0.01 parts by weight of the antioxidant 1010 and 0.02 parts by weight of the antioxidant 168".
The polypropylene materials of examples 1-14 and comparative examples 1-4 were individually tested for performance and the results are shown in Table 2.
TABLE 2
Table 2 (continuation)
As can be seen from the results of the examples, the comparative examples and the table 2, the polypropylene material prepared from the polypropylene composition of the invention has the characteristics of good toughness, high heat resistance, low haze, good fluidity and high-temperature and high-pressure sterilization, and can be used for preparing the prefilled syringe injector.
As can be seen from the results of the tests of comparative examples 1 to 4, the toughness of the resulting polypropylene material increases and the deformation temperature under load decreases slightly as the content of the thermoplastic elastomer in the composition increases.
Comparing the test results of example 1 and example 5, it can be seen that when the thermoplastic elastomer in the composition is a hydrogenated styrene-butadiene-styrene block copolymer, the resulting polypropylene material has better toughness than a polypropylene material prepared using a polyolefin elastomer as the thermoplastic elastomer.
Comparing the test results of example 1 and examples 6-7, it can be seen that the polypropylene material obtained has the best deformation temperature under load when the nucleating agent in the composition is sodium 2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate.
Comparing the test results of example 1 and examples 8-10, it can be seen that the thermoplastic elastomer content in the composition is within the preferred range of the present invention, resulting in a polypropylene material with a higher deformation temperature under load.
As can be seen from the comparison of the test results of example 1 and example 11, when the polypropylene composition adopts the homo-polypropylene with the technical index defined by the invention, the toughness and the heat resistance of the prepared polypropylene material are better.
Comparing the test results of example 1 and example 12, it can be seen that the polypropylene compositions using the thermoplastic elastomer having the specifications defined in the present invention produce polypropylene materials having better toughness.
Comparing the test results of example 1 and example 13, it can be seen that the polypropylene material obtained by using the nucleating agent with the defined specification of the present invention has a higher deformation temperature under load.
Comparing the test results of example 1 and example 14, it can be seen that when the antioxidant used in the polypropylene composition is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butylphenyl) phosphite, the polypropylene material obtained has a longer oxidation induction period and a stronger oxidation resistance when the weight ratio of the two is within the range defined in the present invention.
In comparative example 1, when the content of the homo-polypropylene in the polypropylene composition is out of the range defined in the present invention, the obtained polypropylene material has insufficient toughness and cannot withstand autoclaving.
In comparative example 2, when the content of the thermoplastic elastomer in the polypropylene composition is out of the range defined in the present invention, the resulting polypropylene material has insufficient toughness and cannot withstand autoclaving.
In comparative example 3, when the content of the nucleating agent in the polypropylene composition is out of the range defined in the present invention, the polypropylene material obtained has a low deformation temperature under load and cannot withstand autoclaving.
In comparative example 4, when the content of the antioxidant in the polypropylene composition is out of the range defined in the present invention, the polypropylene material obtained is inferior in oxidation resistance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A polypropylene composition is characterized in that the polypropylene composition contains homopolymerized polypropylene, thermoplastic elastomer, nucleating agent and antioxidant, based on the total weight of the polypropylene composition, the content of the homopolymerized polypropylene is 50-95 wt%, the content of the thermoplastic elastomer is 4-50 wt%, the content of the nucleating agent is 0.05-0.5 wt%, and the content of the antioxidant is 0.05-1 wt%;
wherein the thermoplastic elastomer is selected from at least one of styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, polyolefin elastomer, thermoplastic polyamide, thermoplastic polyurethane and thermoplastic polyester.
2. The composition of claim 1, wherein the homopolypropylene is present in an amount of 65 to 95 wt.%, the thermoplastic elastomer is present in an amount of 4 to 35 wt.%, the nucleating agent is present in an amount of 0.05 to 0.3 wt.%, and the antioxidant is present in an amount of 0.05 to 0.5 wt.%, based on the total weight of the polypropylene composition;
preferably, the homopolypropylene is present in an amount of 75 to 95 wt.%, the thermoplastic elastomer is present in an amount of 4 to 25 wt.%, the nucleating agent is present in an amount of 0.1 to 0.3 wt.%, and the antioxidant is present in an amount of 0.05 to 0.3 wt.%, based on the total weight of the polypropylene composition;
preferably, the thermoplastic elastomer is selected from polyolefin elastomers and/or hydrogenated styrene-butadiene-styrene block copolymers;
preferably, the styrene content in the hydrogenated styrene-butadiene-styrene block copolymer is 5 to 25% by weight, preferably 8 to 20% by weight, more preferably 8 to 15% by weight.
3. The composition of claim 1 or 2, wherein the thermoplastic elastomer has a shore hardness ≦ 90A; preferably, the Shore hardness of the thermoplastic elastomer is less than or equal to 70A;
preferably, the melt mass flow rate of the homopolymerized polypropylene is 1-30g/10min, preferably 5-25g/10min, and more preferably 8-20g/10min at 230 ℃ under the action of 2.16kg load;
preferably, the load deformation temperature of the homopolymerized polypropylene is more than or equal to 85 ℃.
4. The composition according to any one of claims 1 to 3, wherein the nucleating agent is selected from at least one of metal phosphate-based organic nucleating agents, metal carboxylate-based organic nucleating agents and sorbitol derivatives, preferably at least one of sodium 2,2 '-methylenebis (4, 6-di-tert-butylphenyl) phosphate, lithium 2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate, aluminum benzoate, potassium benzoate, lithium benzoate, 1,3,2, 4-dibenzylidene sorbitol, 1,3,2, 4-bis (p-methyldibenzylidene) sorbitol and 1,3,2, 4-bis (3, 4-dimethyldibenzylidene) sorbitol, more preferably 2, at least one of sodium 2 '-methylenebis (4, 6-di-tert-butylphenyl) phosphate, aluminum 2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate and 1,3,2, 4-bis (3, 4-dimethyldibenzylidene) sorbitol;
preferably, the purity of the nucleating agent is more than or equal to 90 percent.
5. The composition according to any one of claims 1 to 4, wherein the antioxidant is selected from the group consisting of pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], n-octadecyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 2, 6-tertiary butyl-4-methylphenol, tris (2, 4-di-t-butylphenyl) phosphite, at least one of bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite and dioctadecyl pentaerythritol diphosphite, preferably pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], n-octadecyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate and tris (2, 4-di-tert-butylphenyl) phosphite, more preferably pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or tris (2, 4-di-tert-butylphenyl) phosphite;
preferably, the weight ratio of the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester to the tri (2, 4-di-tert-butylphenyl) phosphite in the antioxidant is 1: 1-2.
6. A polypropylene material, wherein the polypropylene material is prepared by melt blending and extrusion granulation of the polypropylene composition as defined in any one of claims 1 to 5.
7. A method for preparing a polypropylene material is characterized by comprising the steps of carrying out melt blending on homo-polypropylene, a thermoplastic elastomer, a nucleating agent and an antioxidant, and carrying out extrusion granulation.
8. The method of claim 7, wherein the melt blending conditions comprise: the blending temperature is 25 ℃, the blending time is 1-10min, and the rotation speed is 800-1000 rpm.
9. The method of claim 7 or 8, wherein the conditions of the extrusion granulation comprise: the extrusion temperature is 170-230 ℃, and the rotation speed is 150-200 rpm.
10. Use of a polypropylene material according to claim 6 or prepared by a process according to any one of claims 7 to 9 in a prefilled syringe.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709518A (en) * | 2012-09-29 | 2014-04-09 | 中国石油化工股份有限公司 | Polypropylene composition and polypropylene pellet |
| CN107540951A (en) * | 2016-06-24 | 2018-01-05 | 中国石化扬子石油化工有限公司 | A kind of preparation method of the transparent polypropylene composition with low-temperature impact property |
| CN107841036A (en) * | 2016-09-19 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of polypropene composition and polypropylene material and its application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709518A (en) * | 2012-09-29 | 2014-04-09 | 中国石油化工股份有限公司 | Polypropylene composition and polypropylene pellet |
| CN107540951A (en) * | 2016-06-24 | 2018-01-05 | 中国石化扬子石油化工有限公司 | A kind of preparation method of the transparent polypropylene composition with low-temperature impact property |
| CN107841036A (en) * | 2016-09-19 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of polypropene composition and polypropylene material and its application |
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