CN110540710A - Thermal-aging-resistant polypropylene nano composite material and preparation method thereof - Google Patents
Thermal-aging-resistant polypropylene nano composite material and preparation method thereof Download PDFInfo
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- CN110540710A CN110540710A CN201810543380.1A CN201810543380A CN110540710A CN 110540710 A CN110540710 A CN 110540710A CN 201810543380 A CN201810543380 A CN 201810543380A CN 110540710 A CN110540710 A CN 110540710A
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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Abstract
the invention provides a heat-aging-resistant polypropylene nano composite material and a preparation method thereof, wherein the heat-aging-resistant polypropylene nano composite material is prepared from the following components in parts by weight: 85-92 parts of copolymerized polypropylene, 5-10 parts of toughening agent, 3-5 parts of load type antioxidant and 0.3 part of antioxidant; the supported antioxidant is cerium oxide supported reactive antioxidant nanoparticles. The antioxidant system used in the invention is a compound combination of a nano-load antioxidant, a hindered phenol antioxidant and a thioester antioxidant, and compared with the traditional antioxidant system, the thermal aging resistance of the antioxidant system is greatly improved, and the antioxidant system is reflected in the improvement of the retention rate of mechanical properties after aging, low color difference after aging and the like.
Description
Technical Field
The invention relates to the technical field of modified materials, and particularly relates to a heat-aging-resistant polypropylene nano composite material and a preparation method thereof.
Background
The thermal aging resistance of the material is an important index for testing whether the material can be used and stored for a long time. In the case of polypropylene materials, the thermal aging resistance is poor due to the presence of tertiary carbon atoms in the structure, and a large amount of antioxidant is required to protect the materials from being greatly degraded under high-temperature processing conditions and severe use environments. The common antioxidant is usually hindered phenol or thioester antioxidant, which has poor antioxidant effect, is not resistant to extraction and has larger volatility. Therefore, how to reduce the loss of the low molecular weight antioxidant in the processing, storage and use processes of the polymer material becomes a problem to be solved urgently in the polymer industry.
Disclosure of Invention
The invention aims to provide a thermal aging resistant polypropylene nano composite material and a preparation method thereof.
The technical scheme of the invention is as follows:
The thermal aging resistant polypropylene nano composite material is prepared from the following components in parts by weight:
The supported antioxidant is cerium oxide supported reactive antioxidant nanoparticles.
In a further scheme, the tensile strength of the co-polypropylene is more than or equal to 22MPa, and the notch impact strength is more than or equal to 10KJ/m 2.
The toughening agent is one or a mixture of two of ethylene propylene rubber, ethylene-octene copolymer or chloroprene rubber.
The synthesis method of the cerium oxide supported reactive antioxidant comprises the following steps: drying nano cerium oxide, adding the dried nano cerium oxide into toluene for ultrasonic dispersion, adding gamma-mercaptopropyltriethoxysilane, heating, stirring and refluxing for 3-5h at 90-100 ℃, reducing the temperature of a reaction system to 55-65 ℃, adding an antioxidant, continuously stirring for 1.5-2.5h, performing suction filtration to obtain a solid, and drying to obtain the product.
The antioxidant is 2- [1- (2-hydroxy-3, 5-ditert-butylphenyl) -methylene ] -4, 6-ditert-butylphenyl acrylate (antioxidant GM) or 2- [1- (2-hydroxy-3, 5-ditert-pentylphenyl) ethylene ] -4, 6-ditert-pentylphenyl acrylate (antioxidant GS); the mass ratio of the nano cerium oxide to the gamma-mercaptopropyltriethoxysilane to the antioxidant is 1: 1: 3.
The antioxidant is prepared from tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), tri- (2, 4-di-tert-butylphenyl) phosphite (168) and dioctadecyl thiodipropionate (DSTDP) according to the mass ratio of 2: 2: 1 are mixed.
The invention also aims to provide a preparation method of the heat-aging-resistant polypropylene nano composite material, which comprises the steps of adding 85-92 parts of copolymerized polypropylene, 5-10 parts of toughening agent, 3-5 parts of nano-load antioxidant and 0.3 part of antioxidant into a high-speed mixer for mixing; then adding the uniformly mixed materials into a double-screw extruder, mixing, extruding, cooling and granulating to obtain heat-aging-resistant polypropylene nanocomposite granules; wherein the extrusion temperature of each extrusion zone in the twin-screw extruder is 150-.
Rare earth oxides are widely used in petrochemical and biomedical industries, usually in the form of catalysts. The nano cerium oxide has the characteristics of small crystal grain size, stability and easy dispersion, and is suitable for ultraviolet separants in sunscreen cosmetics, anti-aging agents in plastics and coatings; the crystal lattice is intact, the specific gravity is large, and pores are not easy to form in the ceramic; the product has good dispersibility and transparency, and is easy to be added into polymers such as plastic, silicon rubber and the like.
compared with the traditional material, the composite material prepared by the invention has the following advantages:
(1) the nano-load antioxidant is a composite antioxidant system, antioxidants GM and GS attached to cerium oxide solid particles belong to slow-release antioxidants, free antioxidants are released in time, and the materials can bear instantaneous high temperature in the processing process, so that a part of free antioxidants are additionally added, and the heat resistance at the instantaneous high temperature is improved.
(2) The antioxidant system used in the invention is a compound combination of a nano-load antioxidant, a hindered phenol antioxidant and a thioester antioxidant, and compared with the traditional antioxidant system, the thermal aging resistance of the antioxidant system is greatly improved, and the antioxidant system is reflected in the improvement of the retention rate of mechanical properties after aging, low color difference after aging and the like. Meanwhile, the antioxidant loaded on the filling particles can effectively avoid the pumping loss brought in the material hot processing process, and the weather-resistant aging of the material is improved.
(2) The mechanical property of the composite material is improved by adding the nano cerium oxide particles in the load type antioxidant, and the application range is wider.
Detailed Description
The invention will be further illustrated with reference to specific examples:
the polypropylene copolymer described in the examples has a tensile strength of 22MPa or more and a notched impact strength of 10KJ/m2 or more.
In the embodiment, the toughening agent is one or a mixture of two of ethylene propylene rubber, ethylene-octene copolymer or chloroprene rubber;
In the embodiment, the supported antioxidant is cerium oxide supported reactive antioxidant nanoparticles, and the synthesis method comprises the following steps: drying 10g of nano cerium oxide at 120 ℃ for 4h, ultrasonically dispersing in 500ml of toluene for 20min, then adding 10g of gamma-mercaptopropyltriethoxysilane, and heating, stirring and refluxing at 95 ℃ for 4 h. And after 4h, cooling the reaction system to 60 ℃, adding 30g of antioxidant GM into the reaction system, continuously stirring for 2h, performing suction filtration to obtain a solid, and drying to obtain the cerium oxide-loaded reactive antioxidant nanoparticles.
In the embodiment, the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), tri- (2, 4-di-tert-butylphenyl) phosphite (168), and dioctadecyl thiodipropionate (DSTDP) in a mass ratio of 2: 2: 1.
Example 1
Adding 85 parts of copolymerized polypropylene, 10 parts of toughening agent, 5 parts of load type antioxidant and 0.3 part of antioxidant into a high-speed mixer for mixing for 10 min; then adding the uniformly mixed materials into a double-screw extruder, mixing, extruding, cooling and granulating to obtain heat-aging-resistant polypropylene nanocomposite granules; wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are respectively 150 ℃, 160 ℃, 175 ℃, 185 ℃, 190 ℃ and 200 ℃. The test results are shown in Table 1.
Example 2
Adding 88 parts of polypropylene copolymer, 8 parts of toughening agent, 4 parts of load type antioxidant and 0.3 part of antioxidant into a high-speed mixer for mixing for 10 min; then adding the uniformly mixed materials into a double-screw extruder, mixing, extruding, cooling and granulating to obtain heat-aging-resistant polypropylene nanocomposite granules; wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are 155 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃, 205 ℃ respectively. The test results are shown in Table 1.
Example 3
Adding 92 parts of polypropylene copolymer, 5 parts of toughening agent, 3 parts of load type antioxidant and 0.3 part of antioxidant into a high-speed mixer for mixing for 10 min; then adding the uniformly mixed materials into a double-screw extruder, mixing, extruding, cooling and granulating to obtain heat-aging-resistant polypropylene nanocomposite granules; wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are 160 ℃, 175 ℃, 185 ℃, 195 ℃, 200 ℃, 210 ℃ respectively. The test results are shown in Table 1.
TABLE 1
Comparative example 1
Adding 90 parts of polypropylene copolymer, 10 parts of toughening agent and 0.5 part of antioxidant into a high-speed mixer to mix for 10 min; then adding the uniformly mixed materials into a double-screw extruder, mixing, extruding, cooling and granulating to obtain heat-aging-resistant polypropylene nanocomposite granules; wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are respectively 150 ℃, 160 ℃, 175 ℃, 185 ℃, 190 ℃ and 200 ℃. The test results are shown in Table 2.
comparative example 2
Adding 85 parts of copolymerized polypropylene, 10 parts of toughening agent, 5 parts of nano silicon dioxide supported antioxidant and 0.3 part of antioxidant into a high-speed mixer to mix for 10 min; then adding the uniformly mixed materials into a double-screw extruder, mixing, extruding, cooling and granulating to obtain heat-aging-resistant polypropylene nanocomposite granules; wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are respectively 150 ℃, 160 ℃, 175 ℃, 185 ℃, 190 ℃ and 200 ℃. The test results are shown in Table 2.
TABLE 2
As can be seen from the data in tables 1 and 2, the thermal aging resistance of the thermal aging resistant polypropylene nano composite material prepared by the invention is obviously superior to that of the polypropylene composite material added with a single component antioxidant; meanwhile, the heat aging resistance of the supported antioxidant system adopting other carriers is slightly lower than that of the supported antioxidant system adopting nano cerium oxide as the carrier.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. A thermal aging resistant polypropylene nanocomposite is characterized in that: the composition is prepared from the following components in parts by weight:
85-92 parts of polypropylene copolymer
5-10 parts of toughening agent
3-5 parts of load type antioxidant
0.3 part of antioxidant
The supported antioxidant is cerium oxide supported reactive antioxidant nanoparticles.
2. The thermal aging resistant polypropylene nanocomposite as claimed in claim 1, wherein: the tensile strength of the polypropylene copolymer is more than or equal to 22MPa, and the notch impact strength is more than or equal to 10KJ/m 2.
3. The thermal aging resistant polypropylene nanocomposite as claimed in claim 1, wherein: the toughening agent is one or a mixture of two of ethylene propylene rubber, ethylene-octene copolymer or chloroprene rubber.
4. The thermal aging resistant polypropylene nanocomposite as claimed in claim 1, wherein: the synthesis method of the cerium oxide supported reactive antioxidant comprises the following steps: drying nano cerium oxide, adding the dried nano cerium oxide into toluene for ultrasonic dispersion, adding gamma-mercaptopropyltriethoxysilane, heating, stirring and refluxing for 3-5h at 90-100 ℃, reducing the temperature of a reaction system to 55-65 ℃, adding an oxygen agent, continuously stirring for 1.5-2.5h, performing suction filtration to obtain a solid, and drying to obtain the cerium oxide-based catalyst.
5. The thermal aging resistant polypropylene nanocomposite as claimed in claim 4, wherein: the antioxidant is 2- [1- (2-hydroxy-3, 5-ditert-butylphenyl) -methylene ] -4, 6-ditert-butylphenyl acrylate (antioxidant GM) or 2- [1- (2-hydroxy-3, 5-ditert-pentylphenyl) ethylene ] -4, 6-ditert-pentylphenyl acrylate (antioxidant GS); the mass ratio of the nano cerium oxide to the gamma-mercaptopropyltriethoxysilane to the antioxidant is 1: 1: 3.
6. The thermal aging resistant polypropylene nanocomposite as claimed in claim 1, wherein: the antioxidant is prepared from tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), tri- (2, 4-di-tert-butylphenyl) phosphite (168) and dioctadecyl thiodipropionate (DSTDP) according to the mass ratio of 2: 2: 1 are mixed.
7. The method for preparing a thermal aging resistant polypropylene nanocomposite as claimed in claim 1, wherein: adding 85-92 parts of co-polypropylene, 5-10 parts of toughening agent, 3-5 parts of nano-load antioxidant and 0.3 part of antioxidant into a high-speed mixer for mixing; then adding the uniformly mixed materials into a double-screw extruder, mixing, extruding, cooling and granulating to obtain heat-aging-resistant polypropylene nanocomposite granules; wherein the extrusion temperature of each extrusion zone in the twin-screw extruder is 150-.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717485A (en) * | 2020-05-25 | 2021-11-30 | 合肥杰事杰新材料股份有限公司 | Transparent polymer and preparation method thereof |
| CN114106417A (en) * | 2021-11-08 | 2022-03-01 | 金发科技股份有限公司 | Silane coupling agent modified halloysite nanotube-loaded antioxidant compound, polycarbonate composition, and preparation method and application thereof |
| CN117417250A (en) * | 2023-10-14 | 2024-01-19 | 上海奇克氟硅材料有限公司 | Preparation method of antioxidant and antioxidant |
-
2018
- 2018-05-29 CN CN201810543380.1A patent/CN110540710A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717485A (en) * | 2020-05-25 | 2021-11-30 | 合肥杰事杰新材料股份有限公司 | Transparent polymer and preparation method thereof |
| CN113717485B (en) * | 2020-05-25 | 2022-12-02 | 合肥杰事杰新材料股份有限公司 | Transparent polymer and preparation method thereof |
| CN114106417A (en) * | 2021-11-08 | 2022-03-01 | 金发科技股份有限公司 | Silane coupling agent modified halloysite nanotube-loaded antioxidant compound, polycarbonate composition, and preparation method and application thereof |
| CN117417250A (en) * | 2023-10-14 | 2024-01-19 | 上海奇克氟硅材料有限公司 | Preparation method of antioxidant and antioxidant |
| CN117417250B (en) * | 2023-10-14 | 2024-07-23 | 上海奇克氟硅材料有限公司 | Preparation method of antioxidant and antioxidant |
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