CN116284952A - Preparation method of foaming polypropylene based on supercritical carbon dioxide - Google Patents

Preparation method of foaming polypropylene based on supercritical carbon dioxide Download PDF

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CN116284952A
CN116284952A CN202310326935.8A CN202310326935A CN116284952A CN 116284952 A CN116284952 A CN 116284952A CN 202310326935 A CN202310326935 A CN 202310326935A CN 116284952 A CN116284952 A CN 116284952A
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polypropylene
modified
stirring
carbon dioxide
dopo
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CN116284952B (en
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董卫强
孔凡岳
孔凡琦
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Yangzhou Sparkle Industrial Co ltd
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Yangzhou Sparkle Industrial Co ltd
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2451/00—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
    • C08J2451/06—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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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/00—Use of organic ingredients
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    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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    • 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

Abstract

The invention relates to the field of foaming materials, and discloses a preparation method of foaming polypropylene based on supercritical carbon dioxide. The method comprises the following steps: sequentially modifying polypropylene by 2-hydroxypropyl methacrylate and 3- (methacryloyloxy) propyl trimethoxysilane to obtain modified polypropylene; then 3- (methacryloyloxy) propyl trimethoxy silane is used for modifying the mica powder to obtain modified mica powder; mixing DOPO and GMA to obtain DOPO-GMA, and modifying the ethylene-octene copolymer with DOPO-GMA to obtain a modified ethylene-octene copolymer; and finally, mixing the modified polypropylene, the modified mica powder, the modified ethylene-octene copolymer and the flame retardant, and foaming in supercritical carbon dioxide to prepare the foaming polypropylene. The foamed polypropylene prepared by the invention has small cell size, large cell density, good cell formability, good mechanical property, ageing resistance and flame retardance.

Description

Preparation method of foaming polypropylene based on supercritical carbon dioxide
Technical Field
The invention relates to the field of foaming materials, in particular to a preparation method of foaming polypropylene based on supercritical carbon dioxide.
Background
Polypropylene is one of five general plastics, and has very good heat resistance and mechanical properties. The prepared foaming polypropylene has the characteristics of light weight, good heat preservation, shock resistance, heat resistance, high impact strength, low cost, environmental friendliness and the like through the self-expansion of the polypropylene in the molding process, has excellent cost performance, can be recycled for multiple times, and is an environment-friendly foaming material. Is widely applied to various fields of packaging, automobiles, buildings, communication and the like, and gradually tends to replace other foaming materials.
Conventional polypropylene foaming methods can be generally classified into physical foaming and chemical foaming. With the improvement of requirements on environmental protection, plastic recovery after consumption, product performance price ratio and the like, a physical foaming method mainly comprising physical foaming agents such as carbon dioxide, nitrogen, butane, pentane and the like is widely paid attention to. The carbon dioxide has the characteristics of mild critical condition, higher solubility with polymer, nonflammability, non-toxicity, low price and recycling, has plasticizing and lubricating effects in a polypropylene molecular chain segment, can reduce foaming temperature, and has a good application prospect in preparing foaming polypropylene, and the production process is environment-friendly.
On the other hand, polypropylene belongs to crystalline plastics, has lower melt strength, narrow foaming temperature range and poor foaming performance, and when the processing temperature exceeds the melting point, the melt strength of the polypropylene is extremely fast reduced, the capability of wrapping gas by the melt is reduced, so that foam cells collapse, and qualified foaming products are difficult to prepare. In addition, the polymer is simply foamed, the mechanical properties of the obtained foamed polymer are necessarily reduced to different degrees, and the foamed polymer is difficult to use in severe environments and cannot be used as a structural material, so that the aim of expanding the application range of the foamed polymer material is to realize the reinforcement and toughening of the foamed material, and the improvement of the comprehensive properties of the foamed material is a great problem to be solved.
Chinese patent CN108285574B discloses a foamable polypropylene composition and a foamed polypropylene and a process for preparing the same. The modified polypropylene containing imide group and ether bond or the modified polypropylene containing amide group and ether bond is added into the foamable polypropylene composition to be used as a polymer melt strength modifier, so that the melt strength is enhanced, the foaming performance is improved, and the foamable polypropylene with large foaming multiplying power is prepared by mixing the foamable polypropylene composition with the polypropylene and the foaming agent. However, the patent only enhances the melt strength of polypropylene, improves the foaming performance, does not improve the mechanical properties of the foamed polypropylene, and the foaming agent adopted by the patent is a chemical foaming agent, so that the foaming agent is not environment-friendly.
Chinese patent CN1908053B discloses a method for preparing a silicon-containing polypropylene nano-foaming material by a supercritical carbon dioxide technology, polysiloxane and a compatilizer are added by means of blending modification, the compatilizer is a polymer containing carboxyl, the solubility of the polysiloxane and the compatilizer to carbon dioxide is higher, the addition of the compatilizer greatly induces the nucleation of cells in a PP matrix, simultaneously promotes the growth of the cells, improves the foaming performance, and utilizes the supercritical carbon dioxide technology to prepare the foaming polypropylene, so that the pore structure of the polypropylene foaming material is changed, and the polypropylene foaming material with a fine and uniform nano-porous structure is obtained, but the mechanical property of the prepared polypropylene foaming material is still to be improved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of polypropylene foamed based on supercritical carbon dioxide, which comprises the following steps:
step (1) preparing modified polypropylene, modified mica powder and DOPO-GMA;
wherein, the preparation of the modified polypropylene comprises the following steps:
mixing polypropylene, dimethylbenzene, 2-hydroxypropyl methacrylate, zinc dimethyldithiocarbamate and dicumyl peroxide, heating for reaction in an inert gas environment, and purifying after the reaction to obtain hydroxyl modified polypropylene; adding hydroxyl modified polypropylene into toluene, heating, stirring and refluxing under the protection of inert gas, dropwise adding 3- (methacryloyloxy) propyl trimethoxysilane after the heating, stirring and refluxing are finished, continuously heating, stirring and refluxing are finished, purifying and hydrolyzing to obtain modified polypropylene;
Wherein, the preparation of the modified mica powder comprises the following steps:
stirring, mixing and reacting 3- (methacryloyloxy) propyl trimethoxy silane, ethanol water solution and mica powder, and drying after the reaction is finished to obtain modified mica powder;
wherein, the preparation of DOPO-GMA comprises the following steps:
DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and GMA (glycidyl methacrylate) are mixed and reacted to obtain DOPO-GMA;
step (2) preparing a modified ethylene-octene copolymer;
mixing ethylene-octene copolymer, DOPO-GMA, styrene and dicumyl peroxide, banburying, cooling, granulating and drying after banburying is finished to obtain a modified ethylene-octene copolymer;
step (3) preparing foaming polypropylene;
mixing and banburying modified polypropylene, modified mica powder, modified ethylene-octene copolymer and a flame retardant, and pressing after banburying is finished to obtain a blend sheet; placing the blend sheet sample in an autoclave, firstly introducing carbon dioxide to discharge air in the autoclave, then introducing carbon dioxide, heating to a set pressure and temperature, saturating at the set temperature and pressure, releasing pressure after reaching the saturation time, and cooling to obtain foamed polypropylene;
Wherein the set temperature is 80-120 ℃, and the set pressure is 15-20MPa.
CO 2 The critical temperature is 31.26 ℃, the critical pressure is 72.9atm, and when the carbon dioxide is at a temperature higher than the critical temperature and the pressure is higher than the critical pressure, the property is changedThe density is close to that of liquid, the viscosity is close to that of gas, and the diffusion coefficient is 100 times that of liquid, so that the supercritical fluid is formed.
At the set temperature, when the pressure in the autoclave reaches the set pressure due to the carbon dioxide inlet amount, the pressure is saturated.
Preferably, when the modified polypropylene is prepared in the step (1), the mass ratio of polypropylene, xylene, 2-hydroxypropyl methacrylate, zinc dimethyl dithiocarbamate and dicumyl peroxide is 30:300:0.3:0.24:0.24 (36-45): 2000; the temperature of the heating reaction is 130 ℃, and the time of the heating reaction is 3 hours; the mass ratio of the hydroxyl modified polypropylene to the toluene to the 3- (methacryloxy) propyl trimethoxy silane is (30-31) 500 (1-3), and the temperature of heating, stirring and refluxing is 100 ℃.
Preferably, the inert gas comprises nitrogen.
Preferably, in preparing the hydroxy-modified polypropylene, purification includes precipitation, filtration, and drying.
Further, the precipitation comprises adding the reacted reaction mixture into ethyl acetate, mixing and standing.
Preferably, the purification of the hydroxyl modified polypropylene and the 3- (methacryloyloxy) propyl trimethoxysilane after the dropwise addition, the stirring and the reflux under heating comprises centrifugation and washing, and a centrifugal precipitate after the washing is obtained; the hydrolysis includes adding the washed centrifugal precipitate into ethanol water solution for heating reaction, filtering and drying.
Preferably, the mass percentage of the ethanol in the ethanol water solution is 90%.
Preferably, when the modified mica powder is prepared in the step (1), the mass ratio of the 3- (methacryloyloxy) propyl trimethoxysilane to the ethanol aqueous solution to the mica powder is 3:120-150:1; the mass percentage of ethanol in the ethanol water solution is 90 percent.
Preferably, when the modified mica powder is prepared in the step (1), the speed of stirring and mixing reaction is 800-1200r/min, the temperature of stirring and mixing reaction is 100-130 ℃, and the time of stirring and mixing reaction is 7-20min.
Preferably, in the preparation of DOPO-GMA in the step (1), the mass ratio of DOPO to GMA is 54:35.5; the reaction condition is that the DOPO is reacted for 2 hours after the DOPO is completely dissolved under the constant temperature reaction at the temperature of 95 ℃ and the rotating speed of 30-40 r/min.
Preferably, in the step (2), the mass ratio of the ethylene-octene copolymer to the DOPO-GMA to the styrene to the dicumyl peroxide is 50:2.5:2.5:0.1.
Preferably, in the step (2), the rotation speed of the banburying is 30r/min, the temperature of the banburying is 180 ℃, and the time of the banburying is 5min.
Preferably, in the step (3), the mass ratio of the modified polypropylene to the modified mica powder to the modified ethylene-octene copolymer to the flame retardant is (82-84): 8 (8-10): 33; the flame retardant comprises a mixture of triphenyl methyl phosphate and pentaerythritol, wherein the mass ratio of the triphenyl methyl phosphate to the pentaerythritol is 25:8.
Preferably, in the step (3), the rotation speed of the banburying is 40r/min, the temperature of the banburying is 170-195 ℃ and the time of the banburying is 10min; the pressing plate comprises the following steps: preheating for 3min at 200 ℃, maintaining the pressure for 4min at 12MPa, and then cold-pressing for 5min at 5 MPa; the saturation time is 1-2h; the pressure relief is completed for 2-5s.
Preferably, in the step (3), the total volume of the sample is not more than one twentieth of the volume of the autoclave.
Compared with the prior art, the invention has the following beneficial effects:
the supercritical carbon dioxide kettle pressure foaming effect of the invention is superior to that of the conventional two-step chemical foaming method, and the foaming product has uniform and regular appearance, complete cell structure and higher foaming multiplying power and cell density.
According to the invention, polypropylene is sequentially modified by 2-hydroxypropyl methacrylate and 3- (methacryloyloxy) propyl trimethoxy silane, the 2-hydroxypropyl methacrylate reacts with polypropylene, hydroxyl is introduced into polypropylene molecules to obtain hydroxyl modified polypropylene, the hydroxyl modified polypropylene reacts with 3- (methacryloyloxy) propyl trimethoxy silane to form a long chain branched structure, the melt strength and mechanical property of the modified polypropylene are improved, the foaming property of the polypropylene is further improved, the collapse or merging trend of cells is reduced, and the cell formability is enhanced. Carbonyl groups exist in 2-hydroxypropyl methacrylate and 3- (methacryloyloxy) propyl trimethoxysilane, when the two are grafted to polypropylene, the carbonyl groups are not reacted, but grafted to polypropylene, so that the carbonyl groups exist on the modified polypropylene, the solubility of carbon dioxide in the modified polypropylene is increased by the existence of the carbonyl groups, and a large amount of cell nucleation can be induced by the increased solubility of the carbon dioxide in the polymer, so that the cell density of the foaming material is improved, and the cell size is reduced. In the process of preparing the modified polypropylene, the peroxide can induce the polypropylene to undergo chain scission degradation, and the addition of the zinc dimethyldithiocarbamate can effectively play a role in regulating and controlling, so that the instantaneous concentration of the active free radicals of the system is timely reduced, the service life of the free radicals is prolonged, the degradation of the polypropylene is further delayed, the grafting reaction is promoted, the grafting and degradation reaction of the system is in a controllable range, and the 2-hydroxypropyl methacrylate also has the effect of inhibiting the degradation of the polypropylene. In addition, when hydroxyl modified polypropylene reacts with 3- (methacryloyloxy) propyl trimethoxy silane, the active group methoxy group in the 3- (methacryloyloxy) propyl trimethoxy silane can be directly bonded with hydroxyl groups in hydroxyl modified polypropylene molecules in toluene, and residual methoxy groups are hydrolyzed to introduce-Si-OH on the surface of the modified polypropylene.
According to the invention, the DOPO-GMA is grafted onto the ethylene-octene copolymer, so that carbonyl is introduced, the solubility of carbon dioxide in the ethylene-octene copolymer is increased, the problem of poor affinity between the ethylene-octene copolymer and carbon dioxide is solved, and a large number of foam cells are induced to nucleate, so that the foam cell density of the foaming material is improved, and the size of the foam cells is reduced. And the addition of DOPO gives the ethylene-octene copolymer flame retardance, so that the flame retardance of the finally prepared foamed polypropylene is improved. In addition, the modified ethylene-octene copolymer has excellent propertiesThe melt strength of the glass is equal to the melt strength,the polypropylene composite material has good compatibility with polypropylene, can be uniformly dispersed in polypropylene, improves the integral melt strength of a polypropylene system, reduces the collapse or merging trend of cells, and enhances the cell formability; at the same time, ethylene-octylThe olefin copolymer can generate the effect similar to a nucleating agent to induce the nucleation and foaming of air holes, reduce the foaming process condition of polypropylene and further enhance the stability of cells and the nucleation density. The modified polypropylene has good toughening effect when added into polypropylene, and can improve the impact strength of a polypropylene system. In addition, DOPO-GMA is grafted onto the ethylene-octene copolymer, so that-OH exists on the surface of the modified ethylene-octene copolymer.
According to the invention, the modified mica powder is obtained by modifying the mica powder, and can effectively improve the tensile strength, impact strength, bending strength, dimensional stability and ageing resistance of the foamed polypropylene, and further enhance the melt strength, so that the foaming performance is improved; and 3- (methacryloyloxy) propyl trimethoxy silane is used for modifying the mica powder, so that the agglomeration phenomenon is improved, the dispersibility is enhanced, carbonyl groups exist on the surface of the mica powder, the solubility of carbon dioxide in the mica powder is enhanced, and-Si-OH exists on the surface of the modified mica powder.
the-Si-OH on the surface of the modified mica powder and the-Si-OH on the surface of the modified polypropylene and the-OH on the surface of the modified ethylene-octene copolymer can be dehydrated to generate strong silica bonds, thereby playing a role in reaction compatibilization, improving the bonding force among the interfaces of the modified mica, the modified polypropylene and the modified ethylene-octene copolymer, improving the compatibility and further improving the overall mechanical property of the foamed polypropylene. And carbonyl groups exist on the surfaces of the modified polypropylene, the modified mica powder and the modified ethylene-octene copolymer, so that the solubility of the modified polypropylene, the modified mica powder and the modified ethylene-octene copolymer to carbon dioxide is improved, the foaming in supercritical carbon dioxide is facilitated, and the prepared foaming material has small cell size, large cell density and good cell formability.
In conclusion, the foamed polypropylene prepared by the invention has the advantages of small cell size, large cell density, good cell formability, good mechanical property, ageing resistance and flame retardance.
Drawings
FIG. 1 is a process flow diagram of the present invention for preparing expanded polypropylene;
FIG. 2 is a schematic structural view of the modified polypropylene produced by the present invention;
FIG. 3 is a schematic illustration of the reaction of the present invention to produce modified mica powder;
FIG. 4 is a schematic illustration of a reaction for preparing DOPO-GMA in accordance with the present invention;
FIG. 5 is a schematic illustration of the reaction of the present invention for producing a modified ethylene-octene copolymer.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
The embodiment discloses a preparation method of polypropylene foamed based on supercritical carbon dioxide, which comprises the following steps:
step (1) preparing modified polypropylene, modified mica powder and DOPO-GMA;
Wherein, the preparation of the modified polypropylene comprises the following steps:
mixing polypropylene, dimethylbenzene, 2-hydroxypropyl methacrylate, zinc dimethyldithiocarbamate and dicumyl peroxide according to a mass ratio of 30:300:0.3:0.24:0.24:36:2000, heating to react in a nitrogen environment at 130 ℃ for 3 hours, adding the reaction mixture into ethyl acetate to mix after the reaction, standing for 5 hours, filtering, and drying a filter cake at 80 ℃ for 6 hours to obtain hydroxy modified polypropylene; adding hydroxyl modified polypropylene into toluene, heating, stirring and refluxing under the protection of nitrogen, wherein the temperature of the heating, stirring and refluxing is 100 ℃, the stirring speed of the heating, stirring and refluxing is 300r/min, the heating, stirring and refluxing time is 1h, 3- (methacryloyloxy) propyltrimethoxysilane is dropwise added after the heating, stirring and refluxing is completed, the mass ratio of the hydroxyl modified polypropylene to the toluene to the 3- (methacryloyloxy) propyltrimethoxysilane is 30:500:1, the heating, stirring and refluxing is continued after the dropwise addition is completed, the temperature of the heating, stirring and refluxing is continued at 100 ℃, the stirring speed of the heating, stirring and refluxing is continued at 300r/min, the heating, stirring and refluxing is continued for 3h, the centrifugation at 1500r/min is carried out, the centrifugation sediment is washed for 3 times by absolute ethyl alcohol at room temperature, the washed centrifugation sediment is obtained, the centrifugation sediment after the washing is added into an ethanol hydrothermal solution with the mass percentage of 90%, the centrifugation at 60 ℃ is carried out for 2h, and after the reaction, the filter cake is dried for 6h at 80 ℃ to obtain modified polypropylene;
Wherein, the preparation of the modified mica powder comprises the following steps:
mixing 3- (methacryloyloxy) propyl trimethoxy silane, ethanol aqueous solution with the mass percent of 90% of ethanol and mica powder in a mass ratio of 3:120:1, stirring and mixing at the rotating speed of 800r/min and the temperature of 100 ℃ for 20min, and drying at 80 ℃ for 5h after the reaction is completed to obtain modified mica powder;
wherein, the preparation of DOPO-GMA comprises the following steps:
mixing DOPO and GMA in a mass ratio of 54:35.5, reacting at a constant temperature of 95 ℃ at a rotating speed of 30r/min, and reacting for 2 hours after the DOPO is completely dissolved to obtain DOPO-GMA;
step (2) preparing a modified ethylene-octene copolymer;
mixing an ethylene-octene copolymer, DOPO-GMA, styrene and dicumyl peroxide in a mass ratio of 50:2.5:2.5:0.1, banburying for 5min at the rotating speed of 30r/min and the temperature of 180 ℃, cooling, granulating, and drying at 80 ℃ for 6h to obtain a modified ethylene-octene copolymer;
step (3) preparing foaming polypropylene;
mixing modified polypropylene, modified mica powder, modified ethylene-octene copolymer and flame retardant in a mass ratio of 84:8:8.5:33, banburying for 10min at a rotating speed of 40r/min and a temperature of 170 ℃, pressing the mixture, preheating for 3min at a temperature of 200 ℃, maintaining the pressure for 4min under 12MPa, and cold pressing for 5min under 5MPa to obtain a blend sheet; cutting the blend sheet into a sample with the length and the width of 10mm multiplied by 10mm, and placing the sample in an autoclave, wherein the total volume of the sample is not more than one twentieth of the volume of the autoclave; carbon dioxide is firstly introduced to discharge air in the kettle, then the carbon dioxide is continuously introduced and the temperature is increased until the temperature and the pressure reach 80 ℃ and 15MPa respectively, the temperature and the pressure are saturated for 2 hours at 80 ℃ and 15MPa, then the pressure relief is completed in 2 seconds, and the foamed polypropylene is obtained after cooling.
Example 2
The embodiment discloses a preparation method of polypropylene foamed based on supercritical carbon dioxide, which comprises the following steps:
step (1) preparing modified polypropylene, modified mica powder and DOPO-GMA;
wherein, the preparation of the modified polypropylene comprises the following steps:
mixing polypropylene, dimethylbenzene, 2-hydroxypropyl methacrylate, zinc dimethyldithiocarbamate and dicumyl peroxide according to a mass ratio of 30:300:0.3:0.24:0.24:45:2000, heating to react in a nitrogen environment at 130 ℃ for 3 hours, adding the reaction mixture into ethyl acetate to mix after the reaction, standing for 5 hours, filtering, and drying a filter cake at 85 ℃ for 5 hours to obtain hydroxy modified polypropylene; adding hydroxyl modified polypropylene into toluene, heating, stirring and refluxing under the protection of nitrogen, wherein the temperature of the heating, stirring and refluxing is 100 ℃, the stirring speed of the heating, stirring and refluxing is 300r/min, the heating, stirring and refluxing time is 1h, 3- (methacryloyloxy) propyltrimethoxysilane is dropwise added after the heating, stirring and refluxing is completed, the mass ratio of the hydroxyl modified polypropylene to the toluene to the 3- (methacryloyloxy) propyltrimethoxysilane is 31:500:3, the heating, stirring and refluxing is continued after the dropwise addition is completed, the stirring speed of the heating, stirring and refluxing is continued to be 300r/min, the heating, stirring and refluxing is continued to be 3h, the stirring speed is continued to be 1500r/min after the heating, stirring and refluxing is continued to be completed, the centrifugal precipitate is washed 3 times by absolute ethyl alcohol at room temperature, the washed centrifugal precipitate is obtained, the centrifugal precipitate after washing is added into an ethanol hydrothermal solution with the mass percentage of 90%, the centrifugal precipitate is heated and reacted at 60 ℃ for 2h, filtering, and drying a filter cake is carried out at 85 ℃ for 5h, and modified polypropylene is obtained;
Wherein, the preparation of the modified mica powder comprises the following steps:
mixing 3- (methacryloyloxy) propyl trimethoxy silane, ethanol aqueous solution with the mass percent of 90% of ethanol and mica powder in a mass ratio of 3:150:1, stirring and mixing at the rotation speed of 1200r/min and the temperature of 130 ℃ for 7min, and drying at 80 ℃ for 5h after the reaction is completed to obtain modified mica powder;
wherein, the preparation of DOPO-GMA comprises the following steps:
mixing DOPO and GMA in a mass ratio of 54:35.5, reacting at a constant temperature of 95 ℃ at a rotating speed of 40r/min, and reacting for 2 hours after the DOPO is completely dissolved to obtain DOPO-GMA;
step (2) preparing a modified ethylene-octene copolymer;
mixing an ethylene-octene copolymer, DOPO-GMA, styrene and dicumyl peroxide in a mass ratio of 50:2.5:2.5:0.1, banburying for 5min at the rotating speed of 30r/min and the temperature of 180 ℃, cooling, granulating, and drying at 80 ℃ for 6h to obtain a modified ethylene-octene copolymer;
step (3) preparing foaming polypropylene;
mixing modified polypropylene, modified mica powder, modified ethylene-octene copolymer and flame retardant in a mass ratio of 83.5:8:8:33, banburying for 10min at a rotating speed of 40r/min and a temperature of 195 ℃, pressing the mixture, preheating for 3min at a temperature of 200 ℃, maintaining the pressure for 4min at 12MPa, and cold pressing for 5min at 5MPa to obtain a blend sheet; cutting the blend sheet into a sample with the length and the width of 10mm multiplied by 10mm, and placing the sample in an autoclave, wherein the total volume of the sample is not more than one twentieth of the volume of the autoclave; introducing carbon dioxide to discharge air in the kettle, continuously introducing carbon dioxide and raising the temperature until the temperature and the pressure reach 120 ℃ and 20MPa respectively, saturating for 1h at 120 ℃ and 20MPa, then completing pressure relief in 5s, and cooling to obtain the foamed polypropylene.
Example 3
The embodiment discloses a preparation method of polypropylene foamed based on supercritical carbon dioxide, which comprises the following steps:
step (1) preparing modified polypropylene, modified mica powder and DOPO-GMA;
wherein, the preparation of the modified polypropylene comprises the following steps:
mixing polypropylene, dimethylbenzene, 2-hydroxypropyl methacrylate, zinc dimethyldithiocarbamate and dicumyl peroxide according to a mass ratio of 30:300:0.3:0.24:0.24:37.8.2:2000, heating the mixture in a nitrogen environment for reaction at 130 ℃ for 3 hours, adding the reaction mixture into ethyl acetate for mixing after the reaction, wherein the mass of the ethyl acetate is 7 times that of the dimethylbenzene, standing for 5 hours, filtering, and drying a filter cake at 80 ℃ for 6 hours to obtain hydroxy modified polypropylene; adding hydroxyl modified polypropylene into toluene, heating, stirring and refluxing under the protection of nitrogen, wherein the temperature of the heating, stirring and refluxing is 100 ℃, the stirring speed of the heating, stirring and refluxing is 300r/min, the heating, stirring and refluxing time is 1h, 3- (methacryloyloxy) propyltrimethoxysilane is dropwise added after the heating, stirring and refluxing is completed, the mass ratio of the hydroxyl modified polypropylene to the toluene to the 3- (methacryloyloxy) propyltrimethoxysilane is 30.2:500:1.4, the heating, stirring and refluxing is continued after the dropwise addition is completed, the temperature of the heating, stirring and refluxing is continued to be 100 ℃, the stirring speed of the heating, stirring and refluxing is continued to be 300r/min, the heating, stirring and refluxing is continued to be 3h, the heating, stirring and refluxing is continued to be completed, the centrifugation is 1500r/min, the centrifugation sediment is washed 3 times with absolute ethyl alcohol at room temperature, the washed centrifugation sediment is obtained, the centrifugation sediment after the washing is added into an ethanol hydrothermal solution with the mass percentage of 90%, the heating and reacting for 2h at 60 ℃, filtering, and the filter cake is dried at 80 ℃ for 6h, thus obtaining modified polypropylene;
Wherein, the preparation of the modified mica powder comprises the following steps:
mixing 3- (methacryloyloxy) propyl trimethoxy silane, ethanol aqueous solution with the mass percent of 90% of ethanol and mica powder in a mass ratio of 3:120:1, stirring and mixing at the rotating speed of 1000r/min and the temperature of 120 ℃ for 15min, and drying at 80 ℃ for 5h after the reaction is completed to obtain modified mica powder;
wherein, the preparation of DOPO-GMA comprises the following steps:
mixing DOPO and GMA in a mass ratio of 54:35.5, reacting at a constant temperature of 95 ℃ at a rotating speed of 35r/min, and reacting for 2 hours after the DOPO is completely dissolved to obtain DOPO-GMA;
step (2) preparing a modified ethylene-octene copolymer;
mixing an ethylene-octene copolymer, DOPO-GMA, styrene and dicumyl peroxide in a mass ratio of 50:2.5:2.5:0.1, banburying for 5min at the rotating speed of 30r/min and the temperature of 180 ℃, cooling, granulating, and drying at 80 ℃ for 6h to obtain a modified ethylene-octene copolymer;
step (3) preparing foaming polypropylene;
mixing modified polypropylene, modified mica powder, modified ethylene-octene copolymer and a flame retardant in a mass ratio of 83:8:9:33, banburying for 10min at a rotating speed of 40r/min and a temperature of 180 ℃, pressing the mixture, preheating for 3min at a temperature of 200 ℃, maintaining the pressure for 4min at 12MPa, and cold pressing for 5min at 5MPa to obtain a blend sheet; cutting the blend sheet into a sample with the length and the width of 10mm multiplied by 10mm, and placing the sample in an autoclave, wherein the total volume of the sample is not more than one twentieth of the volume of the autoclave; introducing carbon dioxide to discharge air in the kettle, continuously introducing carbon dioxide and raising the temperature until the temperature and the pressure reach 100 ℃ and 15MPa respectively, saturating for 1.5 hours at 100 ℃ and 15MPa, then completing pressure relief in 2 seconds, and cooling to obtain the foamed polypropylene.
Example 4
The embodiment discloses a preparation method of polypropylene foamed based on supercritical carbon dioxide, which comprises the following steps:
step (1) preparing modified polypropylene, modified mica powder and DOPO-GMA;
wherein, the preparation of the modified polypropylene comprises the following steps:
mixing polypropylene, dimethylbenzene, 2-hydroxypropyl methacrylate, zinc dimethyldithiocarbamate and dicumyl peroxide according to a mass ratio of 30:300:0.3:0.24:0.24:39.6:2000, heating the mixture in a nitrogen environment for reaction at 130 ℃ for 3 hours, adding the reaction mixture into ethyl acetate for mixing after the reaction, wherein the mass of the ethyl acetate is 7 times that of the dimethylbenzene, standing for 5 hours, filtering, and drying a filter cake at 80 ℃ for 6 hours to obtain hydroxy modified polypropylene; adding hydroxyl modified polypropylene into toluene, heating, stirring and refluxing under the protection of nitrogen, wherein the temperature of the heating, stirring and refluxing is 100 ℃, the stirring speed of the heating, stirring and refluxing is 300r/min, the heating, stirring and refluxing time is 1h, 3- (methacryloyloxy) propyltrimethoxysilane is dropwise added after the heating, stirring and refluxing are completed, the mass ratio of the hydroxyl modified polypropylene to the toluene to the 3- (methacryloyloxy) propyltrimethoxysilane is 30.4:500:1.8, the heating, stirring and refluxing are continued after the dropwise addition is completed, the temperature of the heating, stirring and refluxing is continued to be 100 ℃, the stirring speed of the heating, stirring and refluxing is continued to be 300r/min, the heating, stirring and refluxing is continued to be 3h, the heating, stirring and refluxing is continued to be completed, the centrifugation is 1500r/min, the centrifugation sediment is washed 3 times with absolute ethyl alcohol at room temperature, the washed centrifugation sediment is obtained, the centrifugation sediment after the washing is added into an ethanol hydrothermal solution with the mass percentage of 90%, the heating and reacting for 2h at 60 ℃, filtering, and the filter cake is dried at 80 ℃ for 6h, thus obtaining modified polypropylene;
Wherein, the preparation of the modified mica powder comprises the following steps:
mixing 3- (methacryloyloxy) propyl trimethoxy silane, ethanol aqueous solution with the mass percent of 90% of ethanol and mica powder in a mass ratio of 3:130:1, stirring and mixing at the rotating speed of 900r/min and the temperature of 110 ℃ for 18min, and drying at 80 ℃ for 5h after the reaction is completed to obtain modified mica powder;
wherein, the preparation of DOPO-GMA comprises the following steps:
mixing DOPO and GMA in a mass ratio of 54:35.5, reacting at a constant temperature of 95 ℃ at a rotating speed of 30r/min, and reacting for 2 hours after the DOPO is completely dissolved to obtain DOPO-GMA;
step (2) preparing a modified ethylene-octene copolymer;
mixing an ethylene-octene copolymer, DOPO-GMA, styrene and dicumyl peroxide in a mass ratio of 50:2.5:2.5:0.1, banburying for 5min at the rotating speed of 30r/min and the temperature of 180 ℃, cooling, granulating, and drying at 80 ℃ for 6h to obtain a modified ethylene-octene copolymer;
step (3) preparing foaming polypropylene;
mixing modified polypropylene, modified mica powder, modified ethylene-octene copolymer and flame retardant in a mass ratio of 82.5:8:9.5:33, banburying for 10min at a rotating speed of 40r/min and a temperature of 170-195 ℃, pressing the mixture, preheating for 3min at a temperature of 200 ℃, maintaining the pressure for 4min at 12MPa, and cold pressing for 5min at 5MPa to obtain a blend sheet; cutting the blend sheet into a sample with the length and the width of 10mm multiplied by 10mm, and placing the sample in an autoclave, wherein the total volume of the sample is not more than one twentieth of the volume of the autoclave; introducing carbon dioxide to discharge air in the kettle, continuously introducing carbon dioxide and raising the temperature until the temperature and the pressure reach 100 ℃ and 18MPa respectively, saturating for 1.5 hours at 100 ℃ and 18MPa, then completing pressure relief in 2 seconds, and cooling to obtain the foamed polypropylene.
Example 5
The embodiment discloses a preparation method of polypropylene foamed based on supercritical carbon dioxide, which comprises the following steps:
step (1) preparing modified polypropylene, modified mica powder and DOPO-GMA;
wherein, the preparation of the modified polypropylene comprises the following steps:
mixing polypropylene, dimethylbenzene, 2-hydroxypropyl methacrylate, zinc dimethyldithiocarbamate and dicumyl peroxide according to a mass ratio of 30:300:0.3:0.24:0.24:41.4:2000, heating the mixture in a nitrogen environment for reaction at 130 ℃ for 3 hours, adding the reaction mixture into ethyl acetate for mixing after the reaction, wherein the mass of the ethyl acetate is 7 times that of the dimethylbenzene, standing for 5 hours, filtering, and drying a filter cake at 80 ℃ for 6 hours to obtain hydroxy modified polypropylene; adding hydroxyl modified polypropylene into toluene, heating, stirring and refluxing under the protection of nitrogen, wherein the temperature of the heating, stirring and refluxing is 100 ℃, the stirring speed of the heating, stirring and refluxing is 300r/min, the heating, stirring and refluxing time is 1h, 3- (methacryloyloxy) propyltrimethoxysilane is dropwise added after the heating, stirring and refluxing is completed, the mass ratio of the hydroxyl modified polypropylene to the toluene to the 3- (methacryloyloxy) propyltrimethoxysilane is 30.6:500:2.2, the heating, stirring and refluxing is continued after the dropwise addition is completed, the stirring speed of the heating, stirring and refluxing is continued to be 100 ℃, the stirring speed of the heating, stirring and refluxing is continued to be 300r/min, the heating, stirring and refluxing is continued to be 3h, the heating, stirring and refluxing is continued to be completed, the centrifugation is 1500r/min, the centrifugation sediment is washed 3 times with absolute ethyl alcohol at room temperature, the washed centrifugation sediment is obtained, the centrifugation sediment after the washing is added into an ethanol hydrothermal solution with the mass percentage of 90%, the heating and reacting for 2h at 60 ℃, filtering, and the filter cake is dried at 80 ℃ to obtain modified polypropylene;
Wherein, the preparation of the modified mica powder comprises the following steps:
mixing 3- (methacryloyloxy) propyl trimethoxy silane, ethanol aqueous solution with the mass percent of 90% of ethanol and mica powder in a mass ratio of 3:130:1, stirring and mixing at the rotation speed of 1100r/min and the temperature of 125 ℃ for reaction for 10min, and drying at 80 ℃ for 5h after the reaction is completed to obtain modified mica powder;
wherein, the preparation of DOPO-GMA comprises the following steps:
mixing DOPO and GMA in a mass ratio of 54:35.5, reacting at a constant temperature of 95 ℃ at a rotating speed of 35r/min, and reacting for 2 hours after the DOPO is completely dissolved to obtain DOPO-GMA;
step (2) preparing a modified ethylene-octene copolymer;
mixing an ethylene-octene copolymer, DOPO-GMA, styrene and dicumyl peroxide in a mass ratio of 50:2.5:2.5:0.1, banburying for 5min at the rotating speed of 30r/min and the temperature of 180 ℃, cooling, granulating, and drying at 80 ℃ for 6h to obtain a modified ethylene-octene copolymer;
step (3) preparing foaming polypropylene;
mixing modified polypropylene, modified mica powder, modified ethylene-octene copolymer and flame retardant in a mass ratio of 82.2:8:9.8:33, banburying for 10min at a rotating speed of 40r/min and a temperature of 180 ℃, pressing the mixture, preheating for 3min at a temperature of 200 ℃, maintaining the pressure for 4min at 12MPa, and cold pressing for 5min at 5MPa to obtain a blend sheet; cutting the blend sheet into a sample with the length and the width of 10mm multiplied by 10mm, and placing the sample in an autoclave, wherein the total volume of the sample is not more than one twentieth of the volume of the autoclave; introducing carbon dioxide to discharge air in the kettle, continuously introducing carbon dioxide and raising the temperature until the temperature and the pressure reach 100 ℃ and 15MPa respectively, saturating for 2 hours at 100 ℃ and 15MPa, then completing pressure relief in 2 seconds, and cooling to obtain the foamed polypropylene.
Example 6
The embodiment discloses a preparation method of polypropylene foamed based on supercritical carbon dioxide, which comprises the following steps:
step (1) preparing modified polypropylene, modified mica powder and DOPO-GMA;
wherein, the preparation of the modified polypropylene comprises the following steps:
mixing polypropylene, dimethylbenzene, 2-hydroxypropyl methacrylate, zinc dimethyldithiocarbamate and dicumyl peroxide according to a mass ratio of 30:300:0.3:0.24:0.24:43.2:2000, heating the mixture in a nitrogen environment for reaction at 130 ℃ for 3 hours, adding the reaction mixture into ethyl acetate for mixing after the reaction, wherein the mass of the ethyl acetate is 7 times that of the dimethylbenzene, standing for 5 hours, filtering, and drying a filter cake at 80 ℃ for 6 hours to obtain hydroxy modified polypropylene; adding hydroxyl modified polypropylene into toluene, heating, stirring and refluxing under the protection of nitrogen, wherein the temperature of the heating, stirring and refluxing is 100 ℃, the stirring speed of the heating, stirring and refluxing is 300r/min, the heating, stirring and refluxing time is 1h, 3- (methacryloyloxy) propyltrimethoxysilane is dropwise added after the heating, stirring and refluxing is completed, the mass ratio of the hydroxyl modified polypropylene to the toluene to the 3- (methacryloyloxy) propyltrimethoxysilane is 30.8:500:2.6, the heating, stirring and refluxing is continued after the dropwise addition is completed, the stirring speed of the heating, stirring and refluxing is continued to be 100 ℃, the stirring speed of the heating, stirring and refluxing is continued to be 300r/min, the heating, stirring and refluxing is continued to be 3h, the heating, stirring and refluxing is continued to be completed, the centrifugation is 1500r/min, the centrifugation sediment is washed 3 times with absolute ethyl alcohol at room temperature, the washed centrifugation sediment is obtained, the centrifugation sediment after the washing is added into an ethanol hydrothermal solution with the mass percentage of 90%, the heating and reacting for 2h at 60 ℃, filtering, and the filter cake is dried at 80 ℃ to obtain modified polypropylene;
Wherein, the preparation of the modified mica powder comprises the following steps:
mixing 3- (methacryloyloxy) propyl trimethoxy silane, ethanol aqueous solution with the mass percent of 90% of ethanol and mica powder in a mass ratio of 3:130:1, stirring and mixing at the rotation speed of 1100r/min and the temperature of 125 ℃ for reaction for 10min, and drying at 80 ℃ for 5h after the reaction is completed to obtain modified mica powder;
wherein, the preparation of DOPO-GMA comprises the following steps:
mixing DOPO and GMA in a mass ratio of 54:35.5, reacting at a constant temperature of 95 ℃ at a rotating speed of 35r/min, and reacting for 2 hours after the DOPO is completely dissolved to obtain DOPO-GMA;
step (2) preparing a modified ethylene-octene copolymer;
mixing an ethylene-octene copolymer, DOPO-GMA, styrene and dicumyl peroxide in a mass ratio of 50:2.5:2.5:0.1, banburying for 5min at the rotating speed of 30r/min and the temperature of 180 ℃, cooling, granulating, and drying at 80 ℃ for 6h to obtain a modified ethylene-octene copolymer;
step (3) preparing foaming polypropylene;
mixing modified polypropylene, modified mica powder, a modified ethylene-octene copolymer and a flame retardant in a mass ratio of 82:8:10:33, banburying for 10min at a rotating speed of 40r/min and a temperature of 180 ℃, pressing the mixture, preheating for 3min at a temperature of 200 ℃, maintaining the pressure for 4min at 12MPa, and cold pressing for 5min at 5MPa to obtain a blend sheet; cutting the blend sheet into a sample with the length and the width of 10mm multiplied by 10mm, and placing the sample in an autoclave, wherein the total volume of the sample is not more than one twentieth of the volume of the autoclave; introducing carbon dioxide to discharge air in the kettle, continuously introducing carbon dioxide and raising the temperature until the temperature and the pressure reach 100 ℃ and 15MPa respectively, saturating for 2 hours at 100 ℃ and 15MPa, then completing pressure relief in 2 seconds, and cooling to obtain the foamed polypropylene.
Comparative example 1
The comparative example discloses a preparation method of polypropylene foamed based on supercritical carbon dioxide, which comprises the following steps:
step (1) preparing modified mica powder and DOPO-GMA;
wherein, the preparation of the modified mica powder comprises the following steps:
mixing 3- (methacryloyloxy) propyl trimethoxy silane, ethanol aqueous solution with the mass percent of 90% of ethanol and mica powder in a mass ratio of 3:120:1, stirring and mixing at the rotating speed of 1000r/min and the temperature of 120 ℃ for 15min, and drying at 80 ℃ for 5h after the reaction is completed to obtain modified mica powder;
wherein, the preparation of DOPO-GMA comprises the following steps:
mixing DOPO and GMA in a mass ratio of 54:35.5, reacting at a constant temperature of 95 ℃ at a rotating speed of 35r/min, and reacting for 2 hours after the DOPO is completely dissolved to obtain DOPO-GMA;
step (2) preparing a modified ethylene-octene copolymer;
mixing an ethylene-octene copolymer, DOPO-GMA, styrene and dicumyl peroxide in a mass ratio of 50:2.5:2.5:0.1, banburying for 5min at the rotating speed of 30r/min and the temperature of 180 ℃, cooling, granulating, and drying at 80 ℃ for 6h to obtain a modified ethylene-octene copolymer;
step (3) preparing foaming polypropylene;
Mixing polypropylene, modified mica powder, modified ethylene-octene copolymer and flame retardant in a mass ratio of 83:8:9:33, banburying for 10min at a rotating speed of 40r/min and a temperature of 180 ℃, pressing the mixture, preheating for 3min at a temperature of 200 ℃, maintaining the pressure for 4min at 12MPa, and cold pressing for 5min at 5MPa to obtain a blend sheet; cutting the blend sheet into a sample with the length and the width of 10mm multiplied by 10mm, and placing the sample in an autoclave, wherein the total volume of the sample is not more than one twentieth of the volume of the autoclave; introducing carbon dioxide to discharge air in the kettle, continuously introducing carbon dioxide and raising the temperature until the temperature and the pressure reach 100 ℃ and 15MPa respectively, saturating for 1.5 hours at 100 ℃ and 15MPa, then completing pressure relief in 2 seconds, and cooling to obtain the foamed polypropylene.
Comparative example 2
The comparative example discloses a preparation method of polypropylene foamed based on supercritical carbon dioxide, which comprises the following steps:
step (1) preparing modified polypropylene and DOPO-GMA;
wherein, the preparation of the modified polypropylene comprises the following steps:
mixing polypropylene, dimethylbenzene, 2-hydroxypropyl methacrylate, zinc dimethyldithiocarbamate and dicumyl peroxide according to a mass ratio of 30:300:0.3:0.24:0.24:37.8.2:2000, heating the mixture in a nitrogen environment for reaction at 130 ℃ for 3 hours, adding the reaction mixture into ethyl acetate for mixing after the reaction, wherein the mass of the ethyl acetate is 7 times that of the dimethylbenzene, standing for 5 hours, filtering, and drying a filter cake at 80 ℃ for 6 hours to obtain hydroxy modified polypropylene; adding hydroxyl modified polypropylene into toluene, heating, stirring and refluxing under the protection of nitrogen, wherein the temperature of the heating, stirring and refluxing is 100 ℃, the stirring speed of the heating, stirring and refluxing is 300r/min, the heating, stirring and refluxing time is 1h, 3- (methacryloyloxy) propyltrimethoxysilane is dropwise added after the heating, stirring and refluxing is completed, the mass ratio of the hydroxyl modified polypropylene to the toluene to the 3- (methacryloyloxy) propyltrimethoxysilane is 30.2:500:1.4, the heating, stirring and refluxing is continued after the dropwise addition is completed, the temperature of the heating, stirring and refluxing is continued to be 100 ℃, the stirring speed of the heating, stirring and refluxing is continued to be 300r/min, the heating, stirring and refluxing is continued to be 3h, the heating, stirring and refluxing is continued to be completed, the centrifugation is 1500r/min, the centrifugation sediment is washed 3 times with absolute ethyl alcohol at room temperature, the washed centrifugation sediment is obtained, the centrifugation sediment after the washing is added into an ethanol hydrothermal solution with the mass percentage of 90%, the heating and reacting for 2h at 60 ℃, filtering, and the filter cake is dried at 80 ℃ for 6h, thus obtaining modified polypropylene;
Wherein, the preparation of DOPO-GMA comprises the following steps:
mixing DOPO and GMA in a mass ratio of 54:35.5, reacting at a constant temperature of 95 ℃ at a rotating speed of 35r/min, and reacting for 2 hours after the DOPO is completely dissolved to obtain DOPO-GMA;
step (2) preparing a modified ethylene-octene copolymer;
mixing an ethylene-octene copolymer, DOPO-GMA, styrene and dicumyl peroxide in a mass ratio of 50:2.5:2.5:0.1, banburying for 5min at the rotating speed of 30r/min and the temperature of 180 ℃, cooling, granulating, and drying at 80 ℃ for 6h to obtain a modified ethylene-octene copolymer;
step (3) preparing foaming polypropylene;
mixing modified polypropylene, mica powder, a modified ethylene-octene copolymer and a flame retardant in a mass ratio of 83:8:9:33, banburying for 10min at a rotating speed of 40r/min and a temperature of 180 ℃, pressing the mixture, preheating for 3min at a temperature of 200 ℃, maintaining the pressure for 4min at 12MPa, and cold pressing for 5min at 5MPa to obtain a blend sheet; cutting the blend sheet into a sample with the length and the width of 10mm multiplied by 10mm, and placing the sample in an autoclave, wherein the total volume of the sample is not more than one twentieth of the volume of the autoclave; introducing carbon dioxide to discharge air in the kettle, continuously introducing carbon dioxide and raising the temperature until the temperature and the pressure reach 100 ℃ and 15MPa respectively, saturating for 1.5 hours at 100 ℃ and 15MPa, then completing pressure relief in 2 seconds, and cooling to obtain the foamed polypropylene.
Comparative example 3
The comparative example discloses a preparation method of polypropylene foamed based on supercritical carbon dioxide, which comprises the following steps:
step (1) preparing modified polypropylene and modified mica powder;
wherein, the preparation of the modified polypropylene comprises the following steps:
mixing polypropylene, dimethylbenzene, 2-hydroxypropyl methacrylate, zinc dimethyldithiocarbamate and dicumyl peroxide according to a mass ratio of 30:300:0.3:0.24:0.24:37.8.2:2000, heating the mixture in a nitrogen environment for reaction at 130 ℃ for 3 hours, adding the reaction mixture into ethyl acetate for mixing after the reaction, wherein the mass of the ethyl acetate is 7 times that of the dimethylbenzene, standing for 5 hours, filtering, and drying a filter cake at 80 ℃ for 6 hours to obtain hydroxy modified polypropylene; adding hydroxyl modified polypropylene into toluene, heating, stirring and refluxing under the protection of nitrogen, wherein the temperature of the heating, stirring and refluxing is 100 ℃, the stirring speed of the heating, stirring and refluxing is 300r/min, the heating, stirring and refluxing time is 1h, 3- (methacryloyloxy) propyltrimethoxysilane is dropwise added after the heating, stirring and refluxing is completed, the mass ratio of the hydroxyl modified polypropylene to the toluene to the 3- (methacryloyloxy) propyltrimethoxysilane is 30.2:500:1.4, the heating, stirring and refluxing is continued after the dropwise addition is completed, the temperature of the heating, stirring and refluxing is continued to be 100 ℃, the stirring speed of the heating, stirring and refluxing is continued to be 300r/min, the heating, stirring and refluxing is continued to be 3h, the heating, stirring and refluxing is continued to be completed, the centrifugation is 1500r/min, the centrifugation sediment is washed 3 times with absolute ethyl alcohol at room temperature, the washed centrifugation sediment is obtained, the centrifugation sediment after the washing is added into an ethanol hydrothermal solution with the mass percentage of 90%, the heating and reacting for 2h at 60 ℃, filtering, and the filter cake is dried at 80 ℃ for 6h, thus obtaining modified polypropylene;
Wherein, the preparation of the modified mica powder comprises the following steps:
mixing 3- (methacryloyloxy) propyl trimethoxy silane, ethanol aqueous solution with the mass percent of 90% of ethanol and mica powder in a mass ratio of 3:120:1, stirring and mixing at the rotating speed of 1000r/min and the temperature of 120 ℃ for 15min, and drying at 80 ℃ for 5h after the reaction is completed to obtain modified mica powder;
step (2) preparing a modified ethylene-octene copolymer;
mixing an ethylene-octene copolymer, GMA, styrene and dicumyl peroxide in a mass ratio of 50:2.5:2.5:0.1, banburying for 5min at a rotating speed of 30r/min and a temperature of 180 ℃, cooling, granulating, and drying at 80 ℃ for 6h to obtain a modified ethylene-octene copolymer;
step (3) preparing foaming polypropylene;
mixing modified polypropylene, modified mica powder, ethylene-octene copolymer and flame retardant in a mass ratio of 83:8:9:33, banburying for 10min at a rotating speed of 40r/min and a temperature of 180 ℃, pressing the mixture, preheating for 3min at a temperature of 200 ℃, maintaining the pressure for 4min at 12MPa, and cold pressing for 5min at 5MPa to obtain a blend sheet; cutting the blend sheet into a sample with the length and the width of 10mm multiplied by 10mm, and placing the sample in an autoclave, wherein the total volume of the sample is not more than one twentieth of the volume of the autoclave; introducing carbon dioxide to discharge air in the kettle, continuously introducing carbon dioxide and raising the temperature until the temperature and the pressure reach 100 ℃ and 15MPa respectively, saturating for 1.5 hours at 100 ℃ and 15MPa, then completing pressure relief in 2 seconds, and cooling to obtain the foamed polypropylene.
In all the above examples and comparative examples, the particle size of the mica powder was 1250 mesh; DOPO is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and GMA is glycidyl methacrylate; the flame retardant is a mixture of triphenyl methyl phosphate and pentaerythritol, wherein the mass ratio of the triphenyl methyl phosphate to the pentaerythritol is 25:8.
The above comparative example was modified on the basis of example 3, comparative example 1 did not use 2-hydroxypropyl methacrylate, 3- (methacryloyloxy) propyltrimethoxysilane to modify polypropylene; comparative example 2 mica powder was not modified with 3- (methacryloyloxy) propyltrimethoxysilane; comparative example 3 no modification of ethylene-octene copolymer was performed using DOPO-GMA, only GMA was used.
In all the above examples and comparative examples, polypropylene was obtained from petrochemical company, petroleum, lan, china, under the trade designation T30S; xylene is from Shanghai Ala Biochemical technologies Co., ltd, CAS number 1330-20-7;3- (methacryloxy) propyltrimethoxysilane from Hangzhou geochemical company, inc., CAS number 2530-85-0; 2-hydroxypropyl methacrylate is from Tianjin Dike technology Co., ltd, CAS number 923-26-2; zinc dimethyldithiocarbamate is available from Shanghai Yi En chemical technology Co., ltd, CAS number 137-30-4; dicumyl peroxide is derived from Anhui Zesheng Technology Co.,Ltd.CAS number 80-43-3; ethanol is from Shanghai Ala Biochemical technologies Co., ltd, with CAS number 64-17-5; ethyl acetate from shandong rui double chemical industry limited with CAS number 141-78-6; the mica powder is from Baofeng mica processing Co., ltd, model number is 001; DOPO is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide from Zhengzhou alpha chemical Co., ltd, CAS number 35948-25-5; GMA is glycidyl methacrylate from Shanghai Ala Biochemical technology Co., ltd, with CAS number 106-91-2; flame retardants are available from new materials, inc. of Gapeter, guangzhou, model 1010, brand Basoff; ethylene-octene copolymer available from the American Dow group under the designation ENGAGETM8150; styrene from Shanghai Ala Biochemical technologies Co., ltd, CAS number 100-42-5; the trityl phosphate is from Shanghai Michelia Biochemical technologies Co., ltd, with CAS number 1330-78-5; pentaerythritol is fromAnhui Zesheng Technology Co.,Ltd.CAS number 115-77-5.
Test examples
Performance tests were performed on the expanded polypropylene produced in examples 1 to 6 and comparative examples 1 to 3:
1. mechanical properties: testing tensile strength according to national standard GB/T1040.1-2018; bending strength was tested according to national standard GB/T9341-2008; the impact strength of the cantilever beam is tested according to the national standard GB/T1043-2008, and a standard sharp notch sample is adopted;
2. Foaming properties: the average cell size was determined according to national standard GB/T12711-91;
cell density testing: cell density (number of cells per cubic centimeter of material), a photograph obtained by Scanning Electron Microscopy (SEM) was analyzed using computer software (ImageProPlus), wherein 5 SEM photographs at different positions were selected for each sample for analysis, and the number of cells was counted for each sample to be not less than 100, with the following calculation formula:
Figure SMS_1
wherein n is the number of cells on the electron microscope photograph; a is the area (cm) on the photomicrograph 3 ）；ρ p Apparent density (g/cm) of unfoamed material 3 ）；ρ f Apparent density (g/cm) of foam 3 ) The method comprises the steps of carrying out a first treatment on the surface of the The apparent density testing method comprises the following steps: the apparent density of the samples was measured with an automatic density analyzer (AccuPyc 1340 II, micromeritics, USA), 5 samples per group, and the arithmetic average of the results was taken;
3. flame retardant properties: the oxygen index was determined according to the national standard GB/T2406-1993;
the test results are shown in table 1:
TABLE 1
Figure SMS_2
As shown by the test results in Table 1, the foamed polypropylene prepared by the invention has small cell size, large cell density, good cell formability, good mechanical properties, ageing resistance and flame retardance. In comparative example 1, since polypropylene was modified without 2-hydroxypropyl methacrylate, 3- (methacryloyloxy) propyltrimethoxysilane, the modified polypropylene was reduced in melt strength, mechanical properties and foaming properties compared with example 3, in which a long chain branched structure was absent; in comparative example 2, since the mica powder was modified without using 3- (methacryloyloxy) propyltrimethoxysilane, the mechanical properties and foaming properties of the foamed polypropylene were lowered; in comparative example 3, since ethylene-octene copolymer was not modified with DOPO-GMA, ethylene-octene copolymer was modified with only GMA, and flame retardant property of foamed polypropylene was lowered.
The decrease in flame retardant properties of comparative example 3 indicates that the addition of DOPO improves flame retardant properties, and that the mechanical properties of comparative example 3 and the cell size and cell density are not changed because the ethylene-octene copolymer has been modified with GMA, and carbonyl groups have been introduced, so that the foaming properties are not changed much, and further the cell size and cell density are not changed much, but are also decreased because of the decrease in relative molecular mass. And the epoxy group in the GMA can react with the hydroxyl on the surface of the mica to form a chemical bond, so that the reaction compatibilization effect is achieved, and the compatibility between the ethylene-octene copolymer and the polypropylene is good, so that the compatibility between the ethylene-octene copolymer and the polypropylene is still good, the mechanical property is not greatly changed, but the mechanical property is also reduced, and the relative molecular mass is reduced.
The mechanical properties of the foamed polypropylene prepared in comparative example 1 are reduced, the cell size is increased, and the cell density is reduced, which indicates that the modification of polypropylene by using 2-hydroxypropyl methacrylate and 3- (methacryloyloxy) propyl trimethoxysilane improves the mechanical properties of the foamed polypropylene, and the cell size is reduced and the cell density is increased. The modified polypropylene is modified by using 2-hydroxypropyl methacrylate and 3- (methacryloyloxy) propyl trimethoxy silane, a long-chain branched structure is introduced, the mechanical property is improved, and the-Si-OH in the long-chain branched structure reacts with the modified mica powder and the-Si-OH and the-OH on the surface of the modified ethylene-octene copolymer to generate strong silica bonds, so that the effect of reaction compatibilization is achieved, and the mechanical property is further improved; the long-chain branched structure is introduced, so that the melt strength is enhanced, the foaming performance is improved, carbonyl groups are also arranged in the long-chain branched structure, the solubility of polypropylene to carbon dioxide is improved, the foaming performance is further improved, the size of cells is reduced, and the density of the cells is increased.
The mechanical properties of the foamed polypropylene prepared in comparative example 2 are reduced, the cell size is increased, and the cell density is reduced, which shows that the modification of mica powder by using 3- (methacryloyloxy) propyl trimethoxysilane improves the mechanical properties of the foamed polypropylene, the cell size is reduced, and the cell density is increased. This is because when 3- (methacryloyloxy) propyltrimethoxysilane is used for modifying the mica powder, carbonyl is introduced, so that the solubility of the mica powder to carbon dioxide is improved, the foaming performance is improved, the size of the cells is reduced, and the density of the cells is increased; secondly, the reaction between-Si-OH and-Si-OH on the surface of the modified polypropylene and-OH on the surface of the modified ethylene-octene copolymer is introduced, so that a molecule of water is removed, a strong silicon-oxygen bond is generated, the effect of reaction compatibilization is achieved, the mechanical property of the foamed polypropylene is improved, the unmodified mica powder is easy to agglomerate in a system, the foaming is not easy to realize, the dispersion is also not easy to realize, and the mechanical property and the foaming property are reduced.
Compared with the test results of comparative examples 1 and 2, the mechanical properties of comparative example 1 are greatly reduced, the cell size is greatly increased, and the cell density is greatly reduced, because the content of polypropylene in the whole foaming polypropylene system is more than that of mica powder.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1. The preparation method of the polypropylene foamed based on the supercritical carbon dioxide is characterized by comprising the following steps of:
step (1) preparing modified polypropylene, modified mica powder and DOPO-GMA;
wherein, the preparation of the modified polypropylene comprises the following steps:
mixing polypropylene, dimethylbenzene, 2-hydroxypropyl methacrylate, zinc dimethyldithiocarbamate and dicumyl peroxide, heating for reaction in an inert gas environment, and purifying after the reaction to obtain hydroxyl modified polypropylene; adding hydroxyl modified polypropylene into toluene, heating, stirring and refluxing under the protection of inert gas, dropwise adding 3- (methacryloyloxy) propyl trimethoxysilane after the heating, stirring and refluxing are finished, continuously heating, stirring and refluxing are finished, purifying and hydrolyzing to obtain modified polypropylene;
wherein, the preparation of the modified mica powder comprises the following steps:
Stirring, mixing and reacting 3- (methacryloyloxy) propyl trimethoxy silane, ethanol water solution and mica powder, and drying after the reaction is finished to obtain modified mica powder;
wherein, the preparation of DOPO-GMA comprises the following steps:
mixing DOPO and GMA, and reacting to obtain DOPO-GMA;
step (2) preparing a modified ethylene-octene copolymer;
mixing ethylene-octene copolymer, DOPO-GMA, styrene and dicumyl peroxide, banburying, cooling, granulating and drying after banburying is finished to obtain a modified ethylene-octene copolymer;
step (3) preparing foaming polypropylene;
mixing and banburying modified polypropylene, modified mica powder, modified ethylene-octene copolymer and a flame retardant, and pressing after banburying is finished to obtain a blend sheet; and placing the blend sheet sample in an autoclave, introducing carbon dioxide to discharge air in the autoclave, introducing carbon dioxide, heating to a set pressure and temperature, saturating at the set temperature and pressure, releasing pressure after reaching the saturation time, and cooling to obtain the foamed polypropylene.
2. The method for preparing the polypropylene foam based on supercritical carbon dioxide as claimed in claim 1, wherein the mass ratio of polypropylene, xylene, 2-hydroxypropyl methacrylate, zinc dimethyldithiocarbamate and dicumyl peroxide is 30:300:0.3:0.24:0.24 (36-45): 2000; the temperature of the heating reaction is 130 ℃, and the time of the heating reaction is 3 hours; the mass ratio of the hydroxyl modified polypropylene to the toluene to the 3- (methacryloxy) propyl trimethoxy silane is (30-31) 500 (1-3), and the temperature of heating, stirring and refluxing is 100 ℃.
3. The method for preparing the polypropylene foam based on the supercritical carbon dioxide as claimed in claim 1, wherein when the modified mica powder is prepared in the step (1), the mass ratio of the 3- (methacryloyloxy) propyl trimethoxysilane, the ethanol aqueous solution and the mica powder is 3:120-150:1; the mass percentage of ethanol in the ethanol water solution is 90 percent.
4. The method for preparing polypropylene foam based on supercritical carbon dioxide according to claim 1, wherein the speed of stirring and mixing reaction is 800-1200r/min, the temperature of stirring and mixing reaction is 100-130 ℃, and the time of stirring and mixing reaction is 7-20min when the modified mica powder is prepared in the step (1).
5. The method for preparing polypropylene foamed based on supercritical carbon dioxide according to claim 1, wherein the mass ratio of DOPO to GMA in the step (1) is 54:35.5; the reaction condition is that the DOPO is reacted for 2 hours after the DOPO is completely dissolved under the constant temperature reaction at the temperature of 95 ℃ and the rotating speed of 30-40 r/min.
6. The method for preparing polypropylene foam based on supercritical carbon dioxide according to claim 1, wherein in the step (2), the mass ratio of ethylene-octene copolymer, DOPO-GMA, styrene, dicumyl peroxide is 50:2.5:2.5:0.1.
7. The method for preparing polypropylene foamed by supercritical carbon dioxide according to claim 1, wherein in the step (2), the rotation speed of the banburying is 30r/min, the temperature of the banburying is 180 ℃, and the time of the banburying is 5min.
8. The method for preparing the polypropylene foam based on the supercritical carbon dioxide as claimed in claim 1, wherein in the step (3), the mass ratio of the modified polypropylene to the modified mica powder to the modified ethylene-octene copolymer to the flame retardant is (82-84): 8 (8-10): 33; the flame retardant comprises a mixture of triphenyl methyl phosphate and pentaerythritol, wherein the mass ratio of the triphenyl methyl phosphate to the pentaerythritol is 25:8.
9. The method for preparing the polypropylene foam based on the supercritical carbon dioxide according to claim 1, wherein in the step (3), the rotation speed of banburying is 40r/min, the banburying temperature is 170-195 ℃, and the banburying time is 10min; the pressing plate comprises the following steps: preheating for 3min at 200 ℃, maintaining the pressure for 4min at 12MPa, and then cold-pressing for 5min at 5 MPa; the set temperature is 80-120 ℃, and the set pressure is 15-20MPa; the saturation time is 1-2h; the pressure relief is completed for 2-5s.
10. The method for producing a polypropylene foamed on the basis of supercritical carbon dioxide as claimed in claim 1, wherein in the step (3), the total volume of the sample of the blend sheet is not more than one twentieth of the volume of the autoclave.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0362832A (en) * 1989-07-31 1991-03-18 Toray Ind Inc Foamed polyolefin resin and its production
US20040229968A1 (en) * 2003-05-13 2004-11-18 Narasimharao Dontula Manufacturing process for open celled microcellular foam
JP2016191022A (en) * 2015-03-31 2016-11-10 理研ビタミン株式会社 Foaming resin molding
CN115124787A (en) * 2022-08-30 2022-09-30 江苏中科聚合新材料产业技术研究院有限公司 Modified polypropylene foam material and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0362832A (en) * 1989-07-31 1991-03-18 Toray Ind Inc Foamed polyolefin resin and its production
US20040229968A1 (en) * 2003-05-13 2004-11-18 Narasimharao Dontula Manufacturing process for open celled microcellular foam
JP2016191022A (en) * 2015-03-31 2016-11-10 理研ビタミン株式会社 Foaming resin molding
CN115124787A (en) * 2022-08-30 2022-09-30 江苏中科聚合新材料产业技术研究院有限公司 Modified polypropylene foam material and preparation method and application thereof

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