CN111234385B - Polypropylene foaming material based on supercritical carbon dioxide and preparation method thereof - Google Patents
Polypropylene foaming material based on supercritical carbon dioxide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polypropylene foam material based on supercritical carbon dioxide and a preparation method thereof, wherein the polypropylene foam material comprises the following raw materials in parts by weight: 70 to 85 portions of polypropylene resin, 10 to 20 portions of polydimethylsiloxane, 1 to 12 portions of mesoporous silica, 1.5 to 6.5 portions of dispersant, 0.1 to 2 portions of surfactant and 0.1 to 2 portions of antioxidant. The polypropylene foaming material disclosed by the invention is prepared by selecting raw materials, optimizing the content of each raw material and selecting a proper proportion, so that the advantages of the raw materials are fully exerted, and the raw materials are mutually supplemented and promoted, and the prepared polypropylene foaming material based on supercritical carbon dioxide has excellent tensile strength and buffering performance and excellent mechanical performance; high foaming ratio, larger cell density, small cell size, uniform cells and light weight of the foaming material.
Description
Technical Field
The invention relates to the technical field of polypropylene foam materials, in particular to a polypropylene foam material based on supercritical carbon dioxide and a preparation method thereof.
Background
Polypropylene (PP) belongs to thermoplastic resins and is one of five general-purpose resins. The crystal structure is regular, and the crystal structure has the advantages of easy processing, high impact strength, high flexibility resistance, high electric insulation and the like, and is widely applied to the fields of automobile industry, household appliances, electronics, packaging, building material furniture and the like.
Expanded polypropylene (EPP, expanded polypropylene). The polypropylene expanded beads (EPP) are prepared from PP (polypropylene) serving as a main raw material by adopting a physical foaming technology. The foaming and forming die is mainly used for foaming and forming the die into various shapes and sizes for different occasions. The polypropylene expanded product formed by using the polypropylene expanded beads and the mold sintering of the polypropylene expanded beads has many excellent properties compared with the conventional expanded materials such as EPS and EPE.
However, the currently used polypropylene foam materials still have the following problems:
1. the cell size is large and non-uniform;
2. low foaming multiplying power, large relative density and heavy weight;
3. after foaming, the strength is greatly reduced, the mechanical property is poor, and the comprehensive use performance is poor.
Disclosure of Invention
Based on the above situation, the present invention aims to provide a polypropylene foam material based on supercritical carbon dioxide and a preparation method thereof, which can effectively solve the above problems. The polypropylene foaming material is prepared by selecting raw materials, optimizing the content of each raw material, and selecting polypropylene resin, polydimethylsiloxane, mesoporous silica, a dispersing agent, a surfactant and an antioxidant in proper proportion, so that the advantages of the polypropylene resin, the polydimethylsiloxane, the mesoporous silica, the dispersing agent, the surfactant and the antioxidant are fully exerted, and the polypropylene resin, the mesoporous silica, the dispersing agent, the surfactant and the antioxidant complement and promote each other, and the prepared polypropylene foaming material based on the supercritical carbon dioxide has excellent tensile strength and buffering performance and excellent mechanical performance; the foaming multiplying power is high, the foam density is large, the size of the foam is small, the foam is uniform, and the weight of the foaming material is light.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a polypropylene foam material based on supercritical carbon dioxide comprises the following raw materials in parts by weight: 70 to 85 portions of polypropylene resin, 10 to 20 portions of polydimethylsiloxane, 1 to 12 portions of mesoporous silica, 1.5 to 6.5 portions of dispersant, 0.1 to 2 portions of surfactant and 0.1 to 2 portions of antioxidant.
Preferably, the feed comprises the following raw materials in parts by weight: 75 parts of polypropylene resin, 10 parts of polydimethylsiloxane, 5 parts of mesoporous silica, 3 parts of dispersant, 0.8 part of surfactant and 1 part of antioxidant.
Preferably, the polypropylene resin is at least one of blend modified polypropylene, cross-linked or graft modified polypropylene.
Preferably, the mesoporous silica has a pore diameter of 5 to 15nm and a specific surface area of 500 to 800m 2 Per g, pore volume of 0.5-1.5 m 3 /g。
Preferably, the surfactant is any one or a mixture of several of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, cetyl pyridinium chloride and cetyl trimethyl ammonium bromide.
Preferably, the dispersant is an aqueous solution of any one or more of methanol, ethanol, propanol, butanol and pentanol, and the mass fraction of alcohols in the aqueous solution is 50-60%.
Preferably, the antioxidant is 3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid isooctyl ester.
The invention also provides a preparation method of the polypropylene foaming material based on the supercritical carbon dioxide, which comprises the following steps:
1) Weighing the following components in parts by weight: polypropylene resin, polydimethylsiloxane, mesoporous silica, a dispersing agent, a surfactant and an antioxidant;
2) Sequentially adding the weighed polypropylene resin, the dispersant and the surfactant into a high-pressure reaction kettle, stirring and dispersing uniformly, gradually adding polydimethylsiloxane, mesoporous silica and the antioxidant, and stirring uniformly to obtain a polypropylene base material;
3) And continuously introducing low-pressure carbon dioxide into the high-pressure reaction kettle to completely replace air in the kettle, introducing the high-pressure carbon dioxide to ensure that the pressure in the kettle reaches 5.5-8.5 MPa, heating the high-pressure reaction kettle to 110-120 ℃, simultaneously starting the stirring paddle, keeping for 1-3 h under the condition of the pressure of 15.5-18.5 MPa, pre-cooling before pressure relief, then relieving the pressure to normal pressure at the speed of 10-25 MPa/S, and cooling to 10-20 ℃ to obtain the polypropylene foaming material.
Preferably, the temperature of the pre-cooling in the step 3) is reduced by 15 to 30 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the raw materials of the polypropylene foaming material are added with the polydimethylsiloxane in a proper proportion, so that the polypropylene foaming material has good compatibility in a raw material system, is matched with other components, plays a good synergistic effect, greatly accelerates the diffusion speed of a supercritical fluid in a polypropylene base material, and shortens the supercritical CO 2 The diffusion balance time of the fluid in the polypropylene base material greatly improves the production efficiency.
The mesoporous silica with a proper proportion is added into the raw materials of the polypropylene foaming material, so that the polypropylene foaming material has good compatibility in a raw material system, is matched with other components to play a good synergistic effect, and has the advantages of uniform cell size, high cell density, excellent tensile strength and buffering performance and excellent mechanical performance.
The antioxidant is added into the raw materials of the polypropylene foaming material in a proper proportion, so that the polypropylene foaming material has good compatibility in a raw material system, is matched with other components to play a good synergistic effect, has good anti-aging effect and prolongs the service life.
The preparation method has the advantages of simple process, simple and convenient operation, safe and reliable production and low operation cost. The crosslinking reaction process is reacted with supercritical CO 2 The foaming process is carried out separately, no chemical reaction is carried out during foaming, the interference of cross-linking reaction on the nucleation and growth process of foam cells is avoided, the prepared polypropylene foaming material product has small size of the foam cells, high density and uniform distribution, the limitation that only a thin microporous foaming sheet can be prepared in the prior art is broken through, and a polymer microporous foaming plate with larger thickness can be prepared.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description will be given with reference to specific examples, but it should not be construed as limiting the present patent.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.
Example 1:
a polypropylene foaming material based on supercritical carbon dioxide comprises the following raw materials in parts by weight: 70 to 85 portions of polypropylene resin, 10 to 20 portions of polydimethylsiloxane, 1 to 12 portions of mesoporous silica, 1.5 to 6.5 portions of dispersant, 0.1 to 2 portions of surfactant and 0.1 to 2 portions of antioxidant.
In this embodiment, the supercritical carbon dioxide based polypropylene foam material preferably, but not limited to, comprises the following raw materials in parts by weight: 75 parts of polypropylene resin, 10 parts of polydimethylsiloxane, 5 parts of mesoporous silica, 3 parts of dispersant, 0.8 part of surfactant and 1 part of antioxidant.
In the present embodiment, the polypropylene-based resin is preferably, but not limited to, at least one of blend-modified polypropylene, cross-linked or graft-modified polypropylene.
In this embodiment, the mesoporous silica preferably has a pore diameter of, but not limited to, 5 to 15nm and a specific surface area of, but not limited to, 500 to 800m 2 A pore volume of preferably, but not limited to, 0.5 to 1.5m 3 /g。
In this embodiment, the surfactant is preferably, but not limited to, any one or a mixture of sodium dodecylbenzene sulfonate, sodium dodecylsulfonate, sodium dodecylsulfate, cetylpyridinium chloride and cetyltrimethylammonium bromide.
In this embodiment, the dispersant is preferably, but not limited to, an aqueous solution of any one or more of methanol, ethanol, propanol, butanol and pentanol, and the mass fraction of the alcohols in the aqueous solution is preferably, but not limited to, 50 to 60%.
In this embodiment, the antioxidant is preferably, but not limited to, isooctyl 3, 5-di-tert-butyl-4-hydroxyphenylpropionate.
The embodiment also provides a preparation method of the polypropylene foaming material based on the supercritical carbon dioxide, which comprises the following steps:
1) Weighing the following components in parts by weight: polypropylene resin, polydimethylsiloxane, mesoporous silica, a dispersing agent, a surfactant and an antioxidant;
2) Sequentially adding the weighed polypropylene resin, the dispersant and the surfactant into a high-pressure reaction kettle, stirring and dispersing uniformly, gradually adding polydimethylsiloxane, mesoporous silica and the antioxidant, and stirring uniformly to obtain a polypropylene base material;
3) And continuously introducing low-pressure carbon dioxide into the high-pressure reaction kettle to completely displace air in the kettle, introducing the high-pressure carbon dioxide to ensure that the pressure in the kettle reaches 5.5-8.5 MPa, heating the high-pressure reaction kettle to 110-120 ℃, simultaneously starting the stirring paddle, keeping the pressure for 1-3 hours under the condition of 15.5-18.5 MPa, pre-cooling before pressure relief, then relieving the pressure to normal pressure at the speed of 10-25 MPa/S, and cooling to 10-20 ℃ to obtain the polypropylene foaming material.
In this embodiment, the temperature of the pre-cooling in step 3) is reduced by 15 to 30 ℃.
Example 2:
a polypropylene foaming material based on supercritical carbon dioxide comprises the following raw materials in parts by weight: 70 parts of polypropylene resin, 10 parts of polydimethylsiloxane, 3 parts of mesoporous silica, 2.5 parts of dispersant, 0.1 part of surfactant and 0.1 part of antioxidant.
In this example, the polypropylene-based resin was blend-modified polypropylene.
In this embodiment, the mesoporous silica has a pore diameter of 5nm and a specific surface area of 500m 2 Per g, pore volume of 0.5m 3 /g。
In this example, the surfactant is a mixture of sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, and sodium dodecyl sulfate.
In this embodiment, the dispersant is an aqueous solution of methanol and ethanol, and the mass fraction of alcohols in the aqueous solution is 50%.
In this example, the antioxidant is isooctyl 3, 5-di-tert-butyl-4-hydroxyphenylpropionate.
In this embodiment, the preparation method of the polypropylene foam material based on supercritical carbon dioxide comprises the following steps:
1) Weighing the following components in parts by weight: polypropylene resin, polydimethylsiloxane, mesoporous silica, a dispersing agent, a surfactant and an antioxidant;
2) Sequentially adding the weighed polypropylene resin, the dispersant and the surfactant into a high-pressure reaction kettle, stirring and dispersing uniformly, gradually adding polydimethylsiloxane, mesoporous silica and an antioxidant, and stirring uniformly to obtain a polypropylene base material;
3) And continuously introducing low-pressure carbon dioxide into the high-pressure reaction kettle to completely replace air in the kettle, introducing the high-pressure carbon dioxide to ensure that the pressure in the kettle reaches 5.5MPa, heating the high-pressure reaction kettle to 110 ℃, simultaneously starting the stirring paddle, keeping for 1h under the condition of 15.5MPa, pre-cooling before pressure relief, then relieving the pressure to normal pressure at the speed of 10MPa/S, and cooling to 10 ℃ to obtain the polypropylene foaming material.
In this example, the temperature of the pre-cooling in step 3) was reduced by 15 ℃.
Example 3:
a polypropylene foaming material based on supercritical carbon dioxide comprises the following raw materials in parts by weight: 75 parts of polypropylene resin, 10 parts of polydimethylsiloxane, 5 parts of mesoporous silica, 3 parts of dispersant, 0.8 part of surfactant and 1 part of antioxidant.
In this embodiment, the polypropylene-based resin is a crosslinked or graft-modified polypropylene.
In this example, the mesoporous silica has a pore diameter of 10nm and a specific surface area of 800m 2 Per g, pore volume of 1.0m 3 /g。
In this example, the surfactant is a mixture of sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, and sodium dodecyl sulfate.
In this example, the dispersant is an aqueous solution of methanol, wherein the mass fraction of alcohols in the aqueous solution is 55%.
In this example, the antioxidant is isooctyl 3, 5-di-tert-butyl-4-hydroxyphenylpropionate.
In this embodiment, the preparation method of the polypropylene foam material based on supercritical carbon dioxide comprises the following steps:
1) Weighing the following components in parts by weight: polypropylene resin, polydimethylsiloxane, mesoporous silica, a dispersing agent, a surfactant and an antioxidant;
2) Sequentially adding the weighed polypropylene resin, the dispersant and the surfactant into a high-pressure reaction kettle, stirring and dispersing uniformly, gradually adding polydimethylsiloxane, mesoporous silica and an antioxidant, and stirring uniformly to obtain a polypropylene base material;
3) And continuously introducing low-pressure carbon dioxide into the high-pressure reaction kettle to completely replace air in the kettle, introducing the high-pressure carbon dioxide to ensure that the pressure in the kettle reaches 8.5MPa, heating the high-pressure reaction kettle to 115 ℃, simultaneously starting the stirring paddle, keeping for 3 hours under the condition of 18.5MPa, pre-cooling before pressure relief, then relieving the pressure to normal pressure at the speed of 25MPa/S, and cooling to 15 ℃ to obtain the polypropylene foaming material.
In this example, the temperature of the pre-cooling in step 3) was reduced by 20 ℃.
Example 4:
a polypropylene foaming material based on supercritical carbon dioxide comprises the following raw materials in parts by weight: 85 parts of polypropylene resin, 20 parts of polydimethylsiloxane, 5 parts of mesoporous silica, 5 parts of dispersant, 2 parts of surfactant and 2 parts of antioxidant.
In this example, the polypropylene-based resin was blend-modified polypropylene.
In this embodiment, the mesoporous silica has a pore diameter of 15nm and a specific surface area of 500m 2 G, pore volume of 1.5m 3 /g。
In this example, the surfactant is a mixture of sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, and sodium dodecyl sulfate.
In this embodiment, the dispersant is an ethanol aqueous solution, and the mass fraction of alcohols in the aqueous solution is 60%.
In this example, the antioxidant is isooctyl 3, 5-di-tert-butyl-4-hydroxyphenylpropionate.
In this embodiment, the preparation method of the polypropylene foam material based on supercritical carbon dioxide comprises the following steps:
1) Weighing the following components in parts by weight: polypropylene resin, polydimethylsiloxane, mesoporous silica, a dispersing agent, a surfactant and an antioxidant;
2) Sequentially adding the weighed polypropylene resin, the dispersant and the surfactant into a high-pressure reaction kettle, stirring and dispersing uniformly, gradually adding polydimethylsiloxane, mesoporous silica and the antioxidant, and stirring uniformly to obtain a polypropylene base material;
3) And continuously introducing low-pressure carbon dioxide into the high-pressure reaction kettle to completely replace air in the kettle, introducing the high-pressure carbon dioxide to ensure that the pressure in the kettle reaches 8.5MPa, heating the high-pressure reaction kettle to 110 ℃, simultaneously starting the stirring paddle, keeping for 2 hours under the pressure of 17MPa, pre-cooling before pressure relief, then relieving the pressure to normal pressure at the speed of 15MPa/S, and cooling to 15 ℃ to obtain the polypropylene foaming material.
In this example, the temperature of the pre-cooling in step 3) is reduced by 15 ℃.
Comparative example 1:
the difference from example 4 is that there is no mesoporous silica, and the other is the same as example 4.
The following performance tests were performed on the supercritical carbon dioxide based polypropylene foams obtained in examples 2 to 4 of the present invention and comparative example 1 and on a commercially available polypropylene foam, and the internal cell morphology thereof was analyzed by scanning electron microscope analysis and the tensile strength thereof was tested in accordance with the national standard GB/T10654-2001, with the test results shown in table 1.
TABLE 1
From the above table analysis, comparative example 1 and example 4 compare: the mesoporous silica with a proper proportion is added, so that the compatibility in the raw material system of the polypropylene foam material is good, the mesoporous silica is matched with other components to play a good synergistic effect, the molecular weight of polyurethane is increased, and the cells of the polypropylene foam material have uniform cell size, high cell density, excellent tensile strength and buffering performance and excellent mechanical properties.
In conclusion, the polypropylene foam material based on supercritical carbon dioxide of the present invention has excellent performance in all aspects, significantly improves performance, and can greatly meet market demands.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (1)
1. The polypropylene foaming material based on supercritical carbon dioxide is characterized by comprising the following raw materials in parts by weight: 75 parts of polypropylene resin, 10 parts of polydimethylsiloxane, 5 parts of mesoporous silica, 3 parts of dispersant, 0.8 part of surfactant and 1 part of antioxidant;
the polypropylene resin is at least one of blending modified polypropylene and crosslinking or grafting modified polypropylene;
the aperture of the mesoporous silica is 5-15 nm, and the specific surface area is 500-800 m 2 Per g, pore volume of 0.5-1.5 m 3 /g；
The surfactant is any one or a mixture of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, cetyl pyridinium chloride and cetyl trimethyl ammonium bromide;
the dispersing agent is aqueous solution of any one or more of methanol, ethanol, propanol, butanol and pentanol, and the mass fraction of the alcohols in the aqueous solution is 50-60%;
the antioxidant is 3, 5-di-tert-butyl-4-hydroxy-iso-octyl phenylpropionate;
the preparation method of the polypropylene foaming material comprises the following steps:
1) Weighing the following components in parts by weight: polypropylene resin, polydimethylsiloxane, mesoporous silica, a dispersing agent, a surfactant and an antioxidant;
2) Sequentially adding the weighed polypropylene resin, the dispersant and the surfactant into a high-pressure reaction kettle, stirring and dispersing uniformly, gradually adding polydimethylsiloxane, mesoporous silica and an antioxidant, and stirring uniformly to obtain a polypropylene base material;
3) And continuously introducing low-pressure carbon dioxide into the high-pressure reaction kettle to completely replace air in the kettle, introducing the high-pressure carbon dioxide to ensure that the pressure in the kettle reaches 5.5-8.5 MPa, heating the high-pressure reaction kettle to 110-120 ℃, simultaneously starting the stirring paddle, keeping for 1-3 h under the condition of the pressure of 15.5-18.5 MPa, pre-cooling before pressure relief, reducing the temperature of the pre-cooling to 15-30 ℃, then relieving the pressure to normal pressure at the speed of 10-25 MPa/S, and cooling to 10-20 ℃ to obtain the polypropylene foaming material.
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| CN112210113B (en) * | 2020-10-21 | 2022-11-15 | 华东理工大学 | Polypropylene foaming material and preparation method thereof |
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| JP2004269583A (en) * | 2003-03-05 | 2004-09-30 | Idemitsu Petrochem Co Ltd | Thermoplastic resin composition for foaming and its foamed product |
| CN103627076A (en) * | 2012-08-22 | 2014-03-12 | 黑龙江鑫达企业集团有限公司 | Supercritical carbon dioxide kettle pressurization method for preparation of polypropylene foam material |
| CN106146875A (en) * | 2016-07-11 | 2016-11-23 | 浙江新恒泰新材料有限公司 | High-rate thermoplastic polyurethane microporous foamed sheet and production method thereof |
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|---|---|---|---|---|
| JP2004269583A (en) * | 2003-03-05 | 2004-09-30 | Idemitsu Petrochem Co Ltd | Thermoplastic resin composition for foaming and its foamed product |
| CN103627076A (en) * | 2012-08-22 | 2014-03-12 | 黑龙江鑫达企业集团有限公司 | Supercritical carbon dioxide kettle pressurization method for preparation of polypropylene foam material |
| CN106146875A (en) * | 2016-07-11 | 2016-11-23 | 浙江新恒泰新材料有限公司 | High-rate thermoplastic polyurethane microporous foamed sheet and production method thereof |
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