CN114276622B - Heat-resistant transparent polypropylene composition and preparation method and application thereof - Google Patents
Heat-resistant transparent polypropylene composition and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a heat-resistant transparent polypropylene composition, a preparation method and application thereof, wherein the heat-resistant transparent polypropylene composition comprises the following components in parts by weight: 100 parts of polypropylene, 4-8 parts of ethylene-propylene copolymer, 0.1-0.15 part of sodium 2,2' -methylene-bis- (4, 6-di-tert-butylphenyl) phosphate, 0.05-0.1 part of sodium bis (4-tert-butylphenyl) phosphate, 0.2-1 part of antioxidant and 0.1-0.5 part of silicone oil. In the invention, 2' -methylene-bis- (4, 6-di-tert-butylphenyl) sodium phosphate and bis (4-tert-butylphenyl) sodium phosphate are compounded to form a homogeneous system, and the homogeneous system is uniformly dispersed in a random copolymer polypropylene matrix, so that the nucleation density of the random copolymer polypropylene is effectively improved, fine crystals are formed, the mechanical stress is uniformly distributed, and the transparency, heat resistance and mechanical properties of the random copolymer polypropylene are greatly improved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a heat-resistant transparent polypropylene composition, and a preparation method and application thereof.
Background
Polypropylene, PP for short, is a colorless, odorless, nontoxic, semitransparent solid substance. Polypropylene (PP) is a thermoplastic synthetic resin with excellent performance, and is a colorless semitransparent thermoplastic light general-purpose plastic. The polypropylene has chemical resistance, heat resistance, electrical insulation, high strength mechanical property, good high wear resistance processing property and the like, so that the polypropylene is rapidly developed and applied in a plurality of fields of machinery, automobiles, electronic appliances, buildings, textiles, packaging, agriculture, forestry, fishery, food industry and the like since the advent of the prior art. In recent years, with the rapid development of industries such as packaging, electronics, automobiles and the like in China, the development of the industries in China is greatly promoted. Moreover, because of its plasticity, polypropylene materials are gradually replacing wooden products, and high strength toughness and high wear resistance have gradually replaced the mechanical functions of metals.
Transparent agents are a class of additives that are used to improve the light transmission properties of polymers. The polypropylene composition has poor glossiness and transparency, and the appearance is lack of aesthetic feeling, and the development in the fields of transparent packaging and daily necessities is limited. According to the chemical structure, the polypropylene transparent agent mainly comprises dibenzylidene sorbitol and organic phosphate. Wherein: dibenzylidene sorbitol can be dissolved in molten polypropylene to form a homogeneous system, so that the nucleation effect is good, and the disadvantage is that the dibenzylidene sorbitol is unstable at high temperature and is easy to disperse and release parent aromatic aldehyde, so that smell is generated, and the application range of the dibenzylidene sorbitol is limited. The organic phosphate salt has a poor nucleating effect as compared with dibenzylidene sorbitol and has poor dispersibility in polypropylene, but has the advantage of good heat resistance. In order to make the material have excellent heat resistance, the organic phosphate is often selected as a transparent agent, but how to improve the dispersion performance of the organic phosphate in the polypropylene matrix is a technical problem to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a heat-resistant transparent polypropylene composition and a preparation method thereof.
The aim of the invention is realized by the following technical scheme:
the heat-resistant transparent polypropylene composition consists of the following components in parts by weight:
as a preferable technical scheme, the polypropylene is random copolymer polypropylene, and the melt flow rate of the polypropylene is 1-10 g/10min under the test condition of 2.16kg at 230 ℃.
As a preferable technical scheme, the melt flow rate of the ethylene-propylene copolymer is 5-10 g/10min under the test condition of 190 ℃ and 2.16 kg.
As a preferable technical scheme, the antioxidant is a mixture of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionate (1010) and an antioxidant 168. Further, the mixing mass ratio of the tetra [ beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionic acid ] pentaerythritol ester to the antioxidant 168 is 1:1.
As a preferable technical scheme, the lubricant is silicone oil.
Another object of the present invention is to provide a method for preparing the heat-resistant transparent polypropylene composition described above, comprising the steps of:
(1) Adding 100 parts of polypropylene, 4-8 parts of ethylene-propylene copolymer, 0.1-0.15 part of 2,2' -methylene-bis- (4, 6-di-tert-butylphenyl) sodium phosphate, 0.05-0.1 part of sodium bis (4-tert-butylphenyl) phosphate, 0.2-1 part of antioxidant and 0.1-0.5 part of silicone oil into a mixer for uniform mixing to obtain a mixed material;
(2) Adding the mixed material into a double-screw extruder, extruding and granulating to obtain the final product. Further, the temperature of the first area of the twin-screw extruder is 150-160 ℃, the temperature of the second area is 160-180 ℃, the temperature of the third area is 180-200 ℃, the temperature of the fourth area is 200-210 ℃, the temperature of the fifth area is 200-210 ℃, and the temperature of the sixth area is 210-215 ℃.
A third object of the invention is to provide the use of the heat-resistant transparent polypropylene composition described above in the fields of food containers, stationery, films, boxes, bottles, household storages and the like. The heat-resistant transparent polypropylene composition prepared by the invention has excellent transparency, heat resistance and mechanical properties, and can be applied to various fields.
Compared with the prior art, the invention has the beneficial effects that:
in the invention, 2' -methylene-bis- (4, 6-di-tert-butylphenyl) sodium phosphate and bis (4-tert-butylphenyl) sodium phosphate are compounded to form a homogeneous system, and the homogeneous system is uniformly dispersed in a random copolymer polypropylene matrix, so that the nucleation density of the random copolymer polypropylene is effectively improved, fine crystals are formed, the mechanical stress is uniformly distributed, and the transparency, heat resistance and mechanical properties of the random copolymer polypropylene are greatly improved.
Detailed Description
The invention will be further illustrated with reference to examples. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The types and suppliers of the reagents used in the following examples and comparative examples are as follows:
the random copolymer polypropylene was SK R520Y (melt index 1.8g/10 min) from Korea SK company;
the ethylene-propylene copolymer was Tao Shidu to EAA-3003 and had a melt flow rate of 6.5g/10min at 190℃under 2.16kg of test conditions.
The antioxidant is a mixture of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionate (1010) and an antioxidant 168, and the mixing mass ratio is 1:2. The antioxidant tetra [ beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionate ] pentaerythritol ester (1010) and the antioxidant 168 were produced by Basoff, germany.
Sodium 2,2' -methylenebis (4, 6-di-t-butylphenyl) phosphate, sodium bis (4-t-butylphenyl) phosphate, and dibenzylidene sorbitol were all produced by Shandong Mole chemical Co.
It should be noted that the above-mentioned products are for illustrating the sources and components of the reagents used in the experiments of the present invention, so as to be fully disclosed, and do not represent that the present invention cannot be realized by using other reagents of the same kind or provided by other suppliers.
Example 1
(1) 100 parts of random copolymer polypropylene SK R520Y granules, 6 parts of ethylene-propylene copolymer, 0.12 part of 2,2' -methylene-bis- (4, 6-di-tert-butylphenyl) sodium phosphate, 0.08 part of sodium bis (4-tert-butylphenyl) phosphate, 1 part of antioxidant and 0.5 part of silicone oil are added into a mixer to be uniformly mixed;
(2) And adding the uniformly mixed materials into a hopper of a double-screw extruder, extruding and granulating to obtain a final product. The temperature of the first zone of the twin-screw extruder is 150 ℃, the temperature of the second zone is 160 ℃, the temperature of the third zone is 180 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, and the temperature of the sixth zone is 210 ℃.
Example 2
(1) 100 parts of random copolymer polypropylene SK R520Y granules, 8 parts of ethylene-propylene copolymer, 0.15 part of 2,2' -methylene-bis- (4, 6-di-tert-butylphenyl) sodium phosphate, 0.1 part of sodium bis (4-tert-butylphenyl) phosphate, 1 part of antioxidant and 0.5 part of silicone oil are added into a mixer to be uniformly mixed;
(2) And adding the uniformly mixed materials into a hopper of a double-screw extruder, extruding and granulating to obtain a final product. The temperature of the first zone of the twin-screw extruder is 160 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 200 ℃, the temperature of the fourth zone is 210 ℃, the temperature of the fifth zone is 210 ℃, and the temperature of the sixth zone is 215 ℃.
Example 3
(1) 100 parts of random copolymer polypropylene SK R520Y granules, 6 parts of ethylene-propylene copolymer, 0.1 part of 2,2' -methylene-bis- (4, 6-di-tert-butylphenyl) sodium phosphate, 0.1 part of sodium bis (4-tert-butylphenyl) phosphate, 1 part of antioxidant and 0.3 part of silicone oil are added into a mixer to be uniformly mixed;
(2) And adding the uniformly mixed materials into a hopper of a double-screw extruder, extruding and granulating to obtain a final product. The temperature of the first zone of the twin-screw extruder was 155 ℃, the temperature of the second zone was 165 ℃, the temperature of the third zone was 185 ℃, the temperature of the fourth zone was 200 ℃, the temperature of the fifth zone was 210 ℃, and the temperature of the sixth zone was 215 ℃.
Example 4
(1) 100 parts of random copolymer polypropylene SK R520Y granules, 5 parts of ethylene-propylene copolymer, 0.12 part of 2,2' -methylene-bis- (4, 6-di-tert-butylphenyl) sodium phosphate, 0.08 part of sodium bis (4-tert-butylphenyl) phosphate, 0.8 part of antioxidant and 0.4 part of silicone oil are added into a mixer to be uniformly mixed;
(2) And adding the uniformly mixed materials into a hopper of a double-screw extruder, extruding and granulating to obtain a final product. The temperature of the first zone of the twin-screw extruder is 160 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 200 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, and the temperature of the sixth zone is 210 ℃.
Example 5
(1) 100 parts of random copolymer polypropylene SK R520Y granules, 4 parts of ethylene-propylene copolymer, 0.1 part of 2,2' -methylene-bis- (4, 6-di-tert-butylphenyl) sodium phosphate, 0.05 part of sodium bis (4-tert-butylphenyl) phosphate, 0.2 part of antioxidant and 0.1 part of silicone oil are added into a mixer to be uniformly mixed;
(2) And adding the uniformly mixed materials into a hopper of a double-screw extruder, extruding and granulating to obtain a final product. The temperature of the first zone of the twin-screw extruder is 150 ℃, the temperature of the second zone is 160 ℃, the temperature of the third zone is 180 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, and the temperature of the sixth zone is 210 ℃.
Comparative example 1 (in contrast to example 1)
(1) 100 parts of random copolymer polypropylene SK R520Y granules, 6 parts of ethylene-propylene copolymer, 0.2 part of 2,2' -methylene-bis- (4, 6-di-tert-butylphenyl) sodium phosphate, 1 part of antioxidant and 0.5 part of silicone oil are added into a mixer to be uniformly mixed;
(2) And adding the uniformly mixed materials into a hopper of a double-screw extruder, extruding and granulating to obtain a final product. The temperature of the first zone of the twin-screw extruder is 150 ℃, the temperature of the second zone is 160 ℃, the temperature of the third zone is 180 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, and the temperature of the sixth zone is 210 ℃.
Comparative example 2 (in contrast to example 1)
(1) 100 parts of random copolymer polypropylene granules, 6 parts of ethylene-propylene copolymer, 0.2 part of sodium bis (4-tert-butylbenzene) phosphate, 1 part of antioxidant and 0.5 part of silicone oil are added into a mixer to be uniformly mixed;
(2) And adding the uniformly mixed materials into a hopper of a double-screw extruder, extruding and granulating to obtain a final product. The temperature of the first zone of the twin-screw extruder is 150 ℃, the temperature of the second zone is 160 ℃, the temperature of the third zone is 180 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, and the temperature of the sixth zone is 210 ℃.
Comparative example 3 (in contrast to example 1)
(1) 100 parts of homopolymerized polypropylene V30G (medium petrochemical) granules, 6 parts of ethylene-propylene copolymer, 0.12 part of 2,2' -methylene-bis- (4, 6-di-tert-butylphenyl) sodium phosphate, 0.08 part of sodium bis (4-tert-butylphenyl) phosphate, 1 part of antioxidant and 0.5 part of silicone oil are added into a mixer to be uniformly mixed;
(2) And adding the uniformly mixed materials into a hopper of a double-screw extruder, extruding and granulating to obtain a final product. The temperature of the first zone of the twin-screw extruder is 150 ℃, the temperature of the second zone is 160 ℃, the temperature of the third zone is 180 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, and the temperature of the sixth zone is 210 ℃.
Comparative example 4 (in comparison with example 1)
(1) 100 parts of polypropylene PPK7926 (Shanghai Saicaceae, melt finger 28g/10 min) pellet, 6 parts of ethylene-propylene copolymer, 0.12 part of 2,2' -methylene-bis- (4, 6-di-tert-butylphenyl) sodium phosphate, 0.08 part of sodium bis (4-tert-butylphenyl) phosphate, 1 part of antioxidant and 0.5 part of silicone oil are added into a mixer to be uniformly mixed;
(2) And adding the uniformly mixed materials into a hopper of a double-screw extruder, extruding, and granulating. The temperature of the first zone of the twin-screw extruder is 150 ℃, the temperature of the second zone is 160 ℃, the temperature of the third zone is 180 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, and the temperature of the sixth zone is 210 ℃.
Comparative example 5 (in contrast to example 1)
(1) 100 parts of polypropylene BX3920 (Korean SK company, melt index 100g/10 min) pellet, 6 parts of ethylene-propylene copolymer, 0.12 part of sodium 2,2' -methylene-bis- (4, 6-di-tert-butylphenyl) phosphate, 0.08 part of sodium bis (4-tert-butylphenyl) phosphate, 1 part of antioxidant and 0.5 part of silicone oil are added into a mixer to be uniformly mixed;
(2) And adding the uniformly mixed materials into a hopper of a double-screw extruder, extruding and granulating to obtain a final product. The temperature of the first zone of the twin-screw extruder is 150 ℃, the temperature of the second zone is 160 ℃, the temperature of the third zone is 180 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, and the temperature of the sixth zone is 210 ℃.
Comparative example 6 (in contrast to example 1)
(1) 100 parts of random copolymer polypropylene SK R520Y granules, 6 parts of ethylene-propylene copolymer, 0.2 part of dibenzylidene sorbitol, 1 part of antioxidant and 0.5 part of silicone oil are added into a mixer to be uniformly mixed;
(2) And adding the uniformly mixed materials into a hopper of a double-screw extruder, extruding and granulating to obtain a final product. The temperature of the first zone of the twin-screw extruder is 150 ℃, the temperature of the second zone is 160 ℃, the temperature of the third zone is 180 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, and the temperature of the sixth zone is 210 ℃.
Comparative example 7 (in contrast to example 1)
(1) 100 parts of random copolymer polypropylene SK R520Y granules, 6 parts of ethylene-propylene copolymer, 0.12 part of 2,2' -methylene-bis- (4, 6-di-tert-butylphenyl) sodium phosphate, 0.08 part of dibenzylidene sorbitol, 1 part of antioxidant and 0.5 part of silicone oil are added into a mixer to be uniformly mixed;
(2) And adding the uniformly mixed materials into a hopper of a double-screw extruder, extruding and granulating to obtain a final product. The temperature of the first zone of the twin-screw extruder is 150 ℃, the temperature of the second zone is 160 ℃, the temperature of the third zone is 180 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, and the temperature of the sixth zone is 210 ℃.
The results of the performance tests of the products obtained in examples 1 to 5 and comparative examples 1 to 7 are shown in Table 1, in which:
the test conditions of the products prepared in each example and comparative example are as follows:
the tensile bars were (170.0.+ -. 5.0) mm (13.0.+ -. 0.5) mm (3.2.+ -. 0.2) mm, the tensile rate was 5mm/min, test standard GB/T1040.
The type of the cantilever beam notch impact strength spline is as follows: (125.0+ -5.0) mm (13.0+ -0.5) mm (3.2+ -0.2) mm, notch machined, notch depth (2.6+ -0.2) mm, test standard GB/T1843.
The light transmittance test standard is GB/T2680-94.
High temperature discoloration test standard: the sample bars were placed in an aqueous solution at 100 ℃ for 120 hours and, after removal, visually inspected for discoloration.
Table 1 results of performance tests of the products prepared in examples and comparative examples
As can be seen from Table 1, in the invention, the 2,2' -methylene-bis- (4, 6-di-tert-butylphenyl) sodium phosphate and the sodium bis (4-tert-butylphenyl) phosphate are compounded and dissolved in the molten polypropylene to form a homogeneous system, and the homogeneous system is uniformly dispersed in the matrix of the random copolymer polypropylene, so that the nucleation density of the random copolymer polypropylene is effectively improved, fine crystals are formed, the mechanical stress is uniformly distributed, and the transparency, the heat resistance and the mechanical property of the random copolymer polypropylene are greatly improved. In addition, according to the invention, the effect of improving the performance of the random copolymer polypropylene is superior to that of the homo-copolymer polypropylene after the 2,2' -methylene-sodium bis- (4, 6-di-tert-butylphenyl) phosphate and the sodium bis (4-tert-butylphenyl) phosphate are compounded by the comparative example, and the effect of nucleating the copolymer propylene is not obvious.
The product of the invention can be used in food containers, stationery, films, boxes, bottles, household storages, various packages and the like.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent modifications made by the present invention are within the scope of the invention.
Claims (8)
1. A heat resistant transparent polypropylene composition characterized by: the composite material consists of the following components in parts by weight:
the polypropylene is random copolymer polypropylene, and the melt flow rate of the polypropylene is 1-10 g/10min under the test condition of 2.16kg at 230 ℃.
2. The heat-resistant transparent polypropylene composition according to claim 1, wherein: the melt flow rate of the ethylene-propylene copolymer is 5-10 g/10min under the test condition of 190 ℃ and 2.16 kg.
3. The heat-resistant transparent polypropylene composition according to claim 1, wherein: the antioxidant is a mixture of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionate ] and an antioxidant 168.
4. A heat resistant transparent polypropylene composition according to claim 3, wherein: the mixing mass ratio of the tetra [ beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionic acid ] pentaerythritol ester to the antioxidant 168 is 1:1.
5. The heat-resistant transparent polypropylene composition according to claim 1, wherein: the lubricant is silicone oil.
6. A process for the preparation of a heat resistant transparent polypropylene composition according to any of claims 1 to 5, wherein: comprising the following steps:
(1) Adding 100 parts of polypropylene, 4-8 parts of ethylene-propylene copolymer, 0.1-0.15 part of 2,2' -methylene-bis- (4, 6-di-tert-butylphenyl) sodium phosphate, 0.05-0.1 part of sodium bis (4-tert-butylphenyl) phosphate, 0.2-1 part of antioxidant and 0.1-0.5 part of silicone oil into a mixer for uniform mixing to obtain a mixed material;
(2) Adding the mixed material into a double-screw extruder, extruding and granulating to obtain the final product.
7. The method of manufacturing according to claim 6, wherein: the temperature of the first area of the twin-screw extruder is 150-160 ℃, the temperature of the second area is 160-180 ℃, the temperature of the third area is 180-200 ℃, the temperature of the fourth area is 200-210 ℃, the temperature of the fifth area is 200-210 ℃, and the temperature of the sixth area is 210-215 ℃.
8. Use of the heat-resistant transparent polypropylene composition according to any one of claims 1 to 5 in the field of food containers, stationery, films, boxes, bottles, household storages.
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