CN111234385A - 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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- CN111234385A CN111234385A CN202010265067.3A CN202010265067A CN111234385A CN 111234385 A CN111234385 A CN 111234385A CN 202010265067 A CN202010265067 A CN 202010265067A CN 111234385 A CN111234385 A CN 111234385A
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- -1 Polypropylene Polymers 0.000 title claims abstract description 128
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 103
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 103
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000005187 foaming Methods 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 45
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 44
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 34
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 32
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 32
- 239000002270 dispersing agent Substances 0.000 claims abstract description 31
- 239000004094 surface-active agent Substances 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 25
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 239000006261 foam material Substances 0.000 claims abstract description 14
- 239000006260 foam Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229920005673 polypropylene based resin Polymers 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 claims description 3
- 229960001927 cetylpyridinium chloride Drugs 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 230000003139 buffering effect Effects 0.000 abstract description 4
- 230000000295 complement effect Effects 0.000 abstract description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 5
- XSRJBLNNOOTBTM-UHFFFAOYSA-N 6-methylheptyl 2-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)CCCCCOC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 XSRJBLNNOOTBTM-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 210000000497 foam cell Anatomy 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000013012 foaming technology Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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: 70-85 parts of polypropylene resin, 10-20 parts of polydimethylsiloxane, 1-12 parts of mesoporous silica, 1.5-6.5 parts of dispersing agent, 0.1-2 parts of surfactant and 0.1-2 parts 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, the raw materials complement each other 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.
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). The polypropylene expanded beads (EPP) are prepared from PP (polypropylene) serving as a main raw material by adopting a physical foaming technology. The foaming mold is mainly used for foaming and molding a mold into various shapes and sizes for different occasions. The polypropylene expanded products molded by sintering the polypropylene expanded beads and the molds made of the polypropylene expanded beads have many excellent properties as compared with those of conventional expanded materials such as EPS and EPE.
However, the polypropylene foam materials used at present have the following problems:
1. the size of the cells is large and nonuniform;
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 foaming material based on supercritical carbon dioxide comprises the following raw materials in parts by weight: 70-85 parts of polypropylene resin, 10-20 parts of polydimethylsiloxane, 1-12 parts of mesoporous silica, 1.5-6.5 parts of dispersing agent, 0.1-2 parts of surfactant and 0.1-2 parts 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 aperture of the mesoporous silica is 5-15 nm, and the specific surface area is 500-800 m2A pore volume of 0.5 to 1.5 m/g3/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 dispersing agent is an aqueous solution of one or more of methanol, ethanol, propanol, butanol and pentanol, and the mass fraction of the 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 hours under the condition that the pressure is 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 15-30 ℃.
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 CO2The 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 CO2The foaming process is separately carried out, no chemical reaction is carried out during foaming, the interference of a cross-linking reaction on the nucleation and growth process of foam cells is avoided, the size of the foam cells of the prepared polypropylene foaming material product is small, the density is high, the distribution is uniform, the limitation that only a microporous foaming sheet with a thin thickness can be prepared in the prior art is broken through, and a polymer microporous foaming plate with a large 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 of the preferred embodiments of the present invention is provided in connection with specific examples, which 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: 70-85 parts of polypropylene resin, 10-20 parts of polydimethylsiloxane, 1-12 parts of mesoporous silica, 1.5-6.5 parts of dispersing agent, 0.1-2 parts of surfactant and 0.1-2 parts 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 the embodiment, the mesoporous silica preferably has a pore diameter of 5 to 15nm, and a specific surface area of 500 to 800m2The pore volume is preferably but not limited to 0.5 to 1.5m3/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 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 hours under the condition that the pressure is 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 15-30 ℃.
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 example, the mesoporous silica has a pore diameter of 5nm and a specific surface area of 500m2Per g, pore volume of 0.5m3/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 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 5.5MPa, 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) is 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 800m2Per g, pore volume of 1.0m3/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 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 enable the pressure in the kettle to reach 8.5MPa, heating the high-pressure reaction kettle to 115 ℃, simultaneously starting the stirring paddle, keeping for 3 hours under the condition of the pressure of 18.5MPa, pre-cooling before pressure relief, 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) is 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 example, the mesoporous silica has a pore diameter of 15nm and a specific surface area of 500m2G, pore volume of 1.5m3/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 enable the pressure in the kettle to reach 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, relieving the pressure to the 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 no mesoporous silica is present, and the other steps are 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 into a raw material system of the polypropylene foaming material, has good compatibility, is matched with other components, plays a good synergistic effect, is used for increasing the molecular weight of polyurethane, and ensures that the foam pores of the polypropylene foaming material have uniform foam pore size, large foam pore density, excellent tensile strength and buffering performance and excellent mechanical performance.
In conclusion, the polypropylene foaming material based on supercritical carbon dioxide of the present invention has excellent performance in all aspects, significantly improved performance, and can greatly meet the market demand, and in addition, under the comparison, the polypropylene foaming material based on supercritical carbon dioxide prepared in example 3 has the best performance, and the corresponding formula dosage and preparation method thereof are the best schemes.
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 (9)
1. The polypropylene foaming material based on supercritical carbon dioxide is characterized by comprising the following raw materials in parts by weight: 70-85 parts of polypropylene resin, 10-20 parts of polydimethylsiloxane, 1-12 parts of mesoporous silica, 1.5-6.5 parts of dispersing agent, 0.1-2 parts of surfactant and 0.1-2 parts of antioxidant.
2. The supercritical carbon dioxide based polypropylene foam material according to claim 1, 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.
3. The supercritical carbon dioxide-based polypropylene foam according to claim 1, wherein the polypropylene-based resin is at least one of blend-modified polypropylene, cross-linked or graft-modified polypropylene.
4. The supercritical carbon dioxide-based polypropylene foam material according to claim 1, wherein the mesoporous silica has a pore diameter of 5 to 15nm and a specific surface area of 500 to 800m2A pore volume of 0.5 to 1.5 m/g3/g。
5. The supercritical carbon dioxide based polypropylene foam material according to claim 1, wherein the surfactant is any one or a mixture of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, cetyl pyridinium chloride and cetyl trimethyl ammonium bromide.
6. The polypropylene foam material based on supercritical carbon dioxide as claimed in claim 1, wherein the dispersant is 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 50-60%.
7. The supercritical carbon dioxide based polypropylene foam according to claim 1, wherein the antioxidant is isooctyl 3, 5-di-tert-butyl-4-hydroxy phenylpropionate.
8. The method for preparing the polypropylene foaming material based on supercritical carbon dioxide according to any one of claims 1 to 7, 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 hours under the condition that the pressure is 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.
9. The preparation method of the polypropylene foaming material based on supercritical carbon dioxide according to claim 8, wherein the pre-cooling temperature in the step 3) is reduced by 15-30 ℃.
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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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| CN112210113A (en) * | 2020-10-21 | 2021-01-12 | 华东理工大学 | Polypropylene foam material and preparation method thereof |
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