CN110922631A - Preparation method of physical thermal expansion high-molecular foaming agent - Google Patents
Preparation method of physical thermal expansion high-molecular foaming agent Download PDFInfo
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- 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
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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Abstract
The invention discloses a preparation method of a physical thermal expansion high polymer foaming agent, which is prepared by a suspension polymerization method; an oil phase mixture is composed of a monomer, an inert hydrocarbon, an initiator and a cross-linking agent, and a water phase mixture is composed of a dispersing agent, a stabilizing agent, a polymerization inhibitor and deionized water; and mixing the water phase mixture and the oil phase mixture, starting high-speed shearing, and then carrying out suspension polymerization reaction to obtain the physical thermal expansion high-molecular foaming agent. The foaming agent prepared by the invention has light weight and uniform and controllable closed pore structure, and solves the problems of nonuniform pore diameter, uncontrollable gas diffusion and the like generated in the foaming process of the material.
Description
Technical Field
The invention relates to a physical thermal expansion high-molecular foaming agent and a preparation method thereof.
Background
Since the 21 st century, the development of ocean engineering, aerospace, engineering plastics, etc. has become one of the most interesting problems all over the world, and various countries have been paying more attention to the development and optimization of novel lightweight materials. In order to solve the problems of density and strength of the traditional material, the light material can well combine two contradictory characteristics of low density and high strength, and break through the limitation of low specific strength of the traditional material, at present, a method of adding a physical thermal expansion high-molecular foaming agent is adopted at home and abroad to prepare the light material.
The physical thermal expansion high molecular foaming agent is a high molecular particle which has a core-shell structure, the particle diameter is between 5 and 100um, the core is an inert hydrocarbon, and the shell is a thermoplastic polymer. When the microsphere is heated to a certain temperature, the polymer shell is softened, the inert hydrocarbon generates internal vapor pressure to promote the microsphere to expand, and the volume of the expanded particles can be increased to dozens or even hundreds of times of the original volume. After the particles are cooled, the polymer shell is not retracted, and the density is from 400-1200kg/m3Reduced to 20-30kg/m3。
Since the advent of physical thermal expansion polymeric blowing agents, there has been an increasing level of emphasis on these agents. The physical thermal expansion high polymer foaming agent has the greatest advantages of light weight, small, uniform and controllable closed cell structure of the introduced material, and overcomes the problems of different pore sizes, temperature and time dependence during gas diffusion and the like generated in the foaming process of the material. Its another great characteristic is that it has uniform foaming ratio, can make the total density of the whole material reduce under the condition of not influencing the material performance, and make the surface of the formed material more beautiful. At present, the physical thermal expansion high molecular foaming agent is widely applied to the industries of coating printing, foam industry, engineering plastics, leather, papermaking, sealant, paint explosives, cable insulation layers and the like.
As early as the 60's of the 20 th century, Morehouse and Tetreault, the dow chemical, developed thermoplastic expanded microspheres encapsulating a liquid blowing agent using suspension polymerization technology. From the beginning of the 80 s of the 20 th century, a few companies such as aksunobel chemical company in sweden and Songban company in Japan have commercialized a technology for producing a thermal expansion microsphere polymer foaming agent. Over the years, various thermally expandable microsphere polymeric blowing agents have experienced an ongoing progression from manufacture to use. The research shows that the patent applications related to the thermal expansion microsphere high polymer foaming agent in the years 2002-2011 reach the peak, but most of the patents focus on the application of the thermal expansion microsphere high polymer foaming agent in various aspects, and surprisingly, only a small number of the patents discuss the synthesis preparation and the performance of the thermal expansion microsphere high polymer foaming agent. Especially, the research on the domestic physical thermal expansion polymer foaming agent is late, most of the attention points are focused on the application of the foaming agent, and the preparation method is neglected.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a preparation method of a physical thermal expansion high-molecular foaming agent, and the prepared high-molecular foaming agent has complete core-shell structure, uniform particle size distribution, high coating efficiency and good heat resistance of a shell polymer, so that the high-molecular foaming agent is applied to the field of materials to prepare light materials and promote and optimize the further development of the materials.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of a physical thermal expansion high polymer foaming agent comprises the following steps:
1) preparation of oil phase mixture: mixing 90-110 parts by mass of polymerized monomer, 20-40 parts by mass of inert hydrocarbon, 0.1-2.0 parts by mass of initiator and 0.01-1.0 part by mass of cross-linking agent to prepare an oil phase mixture;
2) preparation of aqueous phase mixture: mixing 10-15 parts by mass of a dispersing agent, 0.02-3.0 parts by mass of a stabilizer, 60-100 parts by mass of a polymerization inhibitor and 200-300 parts by mass of deionized water to prepare a water phase mixture;
3) mixing the oil phase mixture and the water phase mixture, and then shearing and stirring at a high speed, wherein the rotating speed is 4000-;
4) suspension polymerization: the reaction temperature is 50-100 ℃, the pressure is 0.1-2.0MPa, and the reaction time is 10-25 h;
5) and (4) carrying out suction filtration, washing and drying to obtain the physical expansion high polymer foaming agent. Is prepared by a suspension polymerization method.
Wherein the polymerization monomer is one or more of acrylonitrile, methacrylonitrile, vinylidene chloride, methyl methacrylate, butyl methacrylate, styrene, acrylic acid, methacrylic acid, hydroxypropyl methacrylate and N, N-dimethylacrylamide.
Wherein the inert hydrocarbon is one or more of isobutane, normal hexane, isopentane, normal pentane, neopentane, isooctane, heptane and petroleum ether.
The crosslinking agent is one or more of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerol diacrylate, glycerol dimethacrylate, PEG200 dimethacrylate, PEG400 dimethacrylate, PEG600 dimethacrylate, trimethylolpropane triacrylate, divinyl ether, 1, 4-butanediol divinyl ether, and divinylbenzene.
Wherein the initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, diacyl peroxide, methyl ethyl ketone peroxide, benzoyl peroxide, lauroyl peroxide and di- (2-ethylhexyl) peroxydicarbonate.
Wherein the dispersant is an inorganic dispersant and/or a water-soluble organic dispersant, wherein the inorganic dispersant is selected from hydroxides and oxides of magnesium, calcium, barium, iron, zinc and manganese; the water soluble dispersant is selected from polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose, hydroxypropyl methylcellulose, carboxymethyl cellulose, silicon dioxide, and agar powder.
The stabilizing agent is a surfactant and is selected from one or more of alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether, tween, sodium dodecyl sulfate and sodium dodecyl sulfate.
Wherein the polymerization inhibitor is one or more of sodium chloride, potassium chloride, magnesium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, ammonium chloride, ammonium sulfate, sodium carbonate and potassium carbonate.
Wherein the temperature of the suspension polymerization reaction is 60-80 ℃, the pressure is 0.4-0.6MPa, and the polymerization reaction time is 15-20 h.
The invention relates to a preparation method of a physical thermal expansion high polymer foaming agent, which is prepared by a suspension polymerization method. An oil phase mixture is composed of a monomer, an inert hydrocarbon, an initiator and a cross-linking agent, and a water phase mixture is composed of a dispersing agent, a stabilizing agent, a polymerization inhibitor and deionized water. Mixing the water phase mixture and the oil phase mixture, and then carrying out high-speed shearing. Under the action of the auxiliary agents such as a dispersing agent, a stabilizing agent, a polymerization inhibitor and the like, the oil phase droplets are uniformly dispersed in water and are broken and split to form stable monomer droplets with uniform diameters. In-situ polymerization reaction is carried out in each droplet at a certain temperature, an initiator in the droplet is decomposed to generate free radicals, and the free radical polymerization gradually forms polymer macromolecules through chain initiation, chain growth, chain termination, chain transfer and the like. Because the polymer macromolecules are not soluble with the foaming agent in the liquid drop, and the polymer macromolecules have certain hydrophilicity, the polymer macromolecules wrap the inert hydrocarbon to gradually form a core-shell structure along with the reaction, and then the polymer macromolecules are further subjected to chain growth and crosslinking to form a stable high molecular substance, and finally the physical expansion high molecular foaming agent is obtained.
The polymeric monomer is required to have excellent heat resistance and a high glass transition temperature Tg, and includes acrylates, nitriles, hydroxyl-containing reactive monomers, amido-containing reactive monomers, carboxyl-containing reactive monomers, and the like. Acrylonitrile, methacrylonitrile, vinylidene chloride, methyl methacrylate, butyl methacrylate, styrene, acrylic acid, methacrylic acid, hydroxypropyl methacrylate, N-dimethylacrylamide are preferred.
The inert hydrocarbon is selected to be a liquid substance having a boiling point below the softening temperature of the thermoplastic polymer shell. According to different foaming temperatures of the physical thermal expansion polymer foaming agent, a C5-C12 linear or branched chain aliphatic saturated hydrocarbon compound is selected, a C5-C8 linear or branched chain saturated hydrocarbon compound is preferred, and one or more of isobutane, normal hexane, isopentane, normal pentane, neopentane, isooctane, heptane, petroleum ether and the like are particularly preferred.
The cross-linking agent comprises two or more polymerizable cross-linking monomers, can expand the elastic range of the polymer and provide a heat stabilizer; including ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerol diacrylate, glycerol dimethacrylate, PEG200 dimethacrylate, PEG400 dimethacrylate, PEG600 dimethacrylate, trimethylolpropane triacrylate, divinyl ether, 1, 4-butanediol divinyl ether, divinylbenzene, etc. Preferably one or more of PEG200 dimethacrylate, PEG400 dimethacrylate, PEG600 dimethacrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane triacrylate.
The initiator is selected from oil-soluble initiators, and the half-life of the initiator is longer. Comprises azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, diacyl peroxide, methyl ethyl ketone peroxide, benzoyl peroxide, lauroyl peroxide, di- (2-ethylhexyl) peroxydicarbonate and the like, and preferably one or more of azobisisobutyronitrile, benzoyl peroxide and lauroyl peroxide.
The substances forming the water phase comprise a dispersant, a stabilizer, a polymerization inhibitor and deionized water.
The dispersing agent may reduce the surface tension between the droplets to facilitate dispersion, reduce or prevent coalescence of the droplets during polymerization. The dispersing agent comprises an inorganic dispersing agent and/or a water-soluble organic dispersing agent, wherein the inorganic dispersing agent comprises hydroxides, oxides and the like of metals such as magnesium, calcium, barium, iron, zinc, manganese and the like, and the water-soluble dispersing agent comprises polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose, hydroxypropyl methylcellulose, carboxymethyl cellulose, silicon dioxide, agar powder and the like. Preferably one or more of nano magnesium hydroxide, nano calcium hydroxide, nano silicon dioxide, polyvinyl alcohol and methyl cellulose.
The stabilizer is a surfactant. Comprises alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether, tween, sodium dodecyl sulfate, etc., preferably one or more of Triton X-100, TX-10, AEO-9 and SDS.
The polymerization inhibitor is inorganic salt, including sodium chloride, potassium chloride, magnesium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, ammonium chloride, ammonium sulfate, sodium carbonate, potassium carbonate, etc., preferably one or more of sodium chloride, potassium chloride and magnesium chloride.
The polymerization conditions include polymerization pressure, polymerization temperature, polymerization duration, and the amount of each reaction raw material added.
The temperature of suspension polymerization is 50-100 ℃, preferably 60-80 ℃;
the pressure of the suspension polymerization is 0.1-2.0MPa, preferably 0.4-0.6 MPa;
the average polymerization time of the physically thermally expandable polymeric blowing agent is 10 to 25 hours, preferably 15 to 20 hours.
In the oil phase mixture, the addition amount of the inert hydrocarbon is 10-50%, preferably 20-40% of the total mass of the polymerized monomers;
the addition amount of the initiator is 0.01 to 3 percent, preferably 0.1 to 2.0 percent of the total mass of the polymerization monomers;
the addition amount of the cross-linking agent is 0.01 to 2 percent, preferably 0.01 to 1.0 percent of the total mass of the polymerization monomers;
in the water phase mixture, the addition amount of the stabilizer is 0.01-1%, preferably 0.1-1.0% of the total mass of the deionized water;
the addition amount of the dispersant is 1-10%, preferably 2-6% of the total mass of the deionized water;
the addition amount of the polymerization inhibitor is 10-45%, preferably 20-40% of the total mass of the deionized water.
The average grain diameter of the prepared physical thermal expansion polymer foaming agent is 5-60um, preferably 5-50 um;
the detailed preparation process of the physical thermal expansion high polymer foaming agent comprises the following steps:
1) forming a shell raw material part of a high-molecular foaming agent by 90-110 parts by mass of a polymerized monomer and 0.01-1.0 part by mass of a cross-linking agent, sequentially adding 20-40 parts by mass of an inert hydrocarbon and 0.1-2.0 parts by mass of an initiator to form a core raw material part of the high-molecular foaming agent, and uniformly mixing all the materials to prepare an oil phase mixture;
2) fully dissolving and uniformly mixing 200-300 parts by mass of deionized water, 0.02-3.0 parts by mass of surfactant, 10-15 parts by mass of dispersant and 60-100 parts by mass of polymerization inhibitor to prepare a water-phase mixture;
3) the prepared oil phase mixture and the prepared water phase mixture are put into a high-speed dispersant, oil phase droplets are uniformly dispersed in the water phase under the high-speed stirring of the rotation speed of 4000-10000r/min, and the diameter of the oil phase droplets is controlled between 5 and 60 mu m through stirring and dispersion;
4) dropping the prepared suspension liquid with uniform dispersion and qualified particle size into a polymerization reaction kettle, introducing nitrogen for protection, starting a stirring device, setting the pressure to be 0.4-0.6MPa, slowly heating to 60-80 ℃, and starting free radical polymerization reaction for 15-20 hours;
5) and (3) carrying out suction filtration on the prepared high molecular polymer, washing for 2-3 times by using deionized water, drying in a vacuum oven, and finally crushing and sieving to prepare the physical expansion high molecular foaming agent.
The physical thermal expansion high-molecular foaming agent is applied to plastics such as polyethylene, polypropylene, polyester, phenolic resin, EVA resin, butadiene rubber, isoprene rubber, nitrile rubber, ethylene propylene rubber, nylon, polyvinyl chloride, polyurethane and the like, so that the high-molecular material has uniform foaming multiplying power, the total density of the material can be reduced under the condition of not influencing the material performance, and a low-density lightweight material is prepared, and the application of a high-molecular material product is wider.
The preparation is carried out by adopting a suspension polymerization method; an oil phase mixture is composed of a monomer, an inert hydrocarbon, an initiator and a cross-linking agent, and a water phase mixture is composed of a dispersing agent, a stabilizing agent, a polymerization inhibitor and deionized water; mixing the water phase mixture and the oil phase mixture, and starting high-speed shearing to break the oil phase droplets into small droplets with uniform diameters. At a certain temperature, the interior of each small drop generates free radical initiation polymerization reaction, and a high molecular foaming agent with a shell of high molecular polymer and low-boiling inert hydrocarbon inside is gradually formed through chain initiation, chain propagation, chain termination, chain transfer and the like. The blowing agent expands immediately upon heating, can expand several tens to several hundreds of times in volume, and does not retract after cooling.
The physical thermal expansion high polymer foaming agent has the performance depending on the type and the amount of the polymerized monomer, the type of the cross-linking agent, the type of the initiator, the type and the amount of the inert hydrocarbon, the size and the morphology of the foaming agent and the like, and the physical thermal expansion high polymer foaming agent with different foaming characteristics and sizes can be prepared by changing the polymerization conditions. The foaming agent prepared by the invention has the greatest advantages of light weight, uniform and controllable closed pore structure, and overcomes the problems of nonuniform pore diameter, uncontrollable gas diffusion and the like generated in the foaming process of the material. And the foaming ratio is uniform, the total density of the whole material is reduced under the condition of not influencing the strength of the material, so that the low-density and light-weight material is prepared, and the formed material surface is more attractive.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents also fall within the scope of the invention.
Example 1
1) Preparation of oil phase mixture
Mixing 50 parts by mass of 1, 1-dichloroethylene, 15 parts by mass of acrylonitrile, 5.0 parts by mass of methacrylonitrile, 29 parts by mass of methyl methacrylate, 1.0 part by mass of styrene, 0.1 part by mass of 1, 6-hexanediol di (meth) acrylate and 0.1 part by mass of trimethylolpropane triacrylate to form a shell raw material part of a high-molecular foaming agent; sequentially adding 15 parts by mass of isobutane, 15 parts by mass of isooctane and 0.6 part by mass of benzoyl peroxide to form a core raw material part of the high-molecular foaming agent, and uniformly mixing all the materials to prepare an oil phase mixture;
2) preparation of aqueous mixtures
Fully dissolving and uniformly mixing 250 parts by mass of deionized water, 0.4 part by mass of non-surfactant triton X-1100.35 parts by mass of sodium dodecyl sulfate, 25 parts by mass of colloidal silicon dioxide with the solid content of 30%, 0.4 part by mass of polyvinylpyrrolidone, 0.02 part by mass of sodium nitrite and 85 parts by mass of sodium chloride to prepare an aqueous phase mixture;
3) putting the prepared oil phase mixture and the prepared water phase mixture into a high-speed dispersing agent, uniformly dispersing oil phase droplets in a water phase under high-speed stirring at the rotating speed of 6000r/min, and controlling the diameter of the oil phase droplets to be between 5 and 60um through stirring and dispersing;
4) dropping the prepared suspension liquid with uniform dispersion and qualified particle size into a polymerization reaction kettle, introducing nitrogen for protection, starting a stirring device, setting the pressure to be 0.4-0.6MPa, slowly heating to 60 ℃, and starting free radical polymerization reaction for 20 hours;
5) and (3) carrying out suction filtration on the prepared high molecular polymer, washing for 2-3 times by using deionized water, drying in a vacuum oven, and finally crushing and sieving to prepare the physical expansion high molecular foaming agent.
Example 2
1) Preparation of oil phase mixture
57 parts by mass of 1, 1-dichloroethylene, 34 parts by mass of methyl methacrylate, 5 parts by mass of acrylonitrile, 3 parts by mass of hydroxyethyl methacrylate, 1.0 part by mass of styrene, 0.2 part by mass of PEG200 dimethacrylate and 0.1 part by mass of divinylbenzene are mixed to form a shell raw material part of the high-molecular foaming agent; sequentially adding 15 parts by mass of neopentane, 20 parts by mass of n-hexane, 0.5 part by mass of benzoyl peroxide and 0.2 part by mass of azodiisobutyronitrile to form a core raw material part of the high-molecular foaming agent, and uniformly mixing all the materials to prepare an oil phase mixture;
2) preparation of aqueous mixtures
Fully dissolving and uniformly mixing 300 parts by mass of deionized water, 90.3 parts by mass of non-surfactant lauryl polyoxyethylene ether AEO-0, 0.3 part by mass of sodium dodecyl benzene sulfonate, 15 parts by mass of nano magnesium hydroxide, 0.5 part by mass of polyvinyl alcohol and 100 parts by mass of sodium chloride to prepare an aqueous phase mixture;
3) putting the prepared oil phase mixture and the prepared water phase mixture into a high-speed dispersing agent, uniformly dispersing oil phase droplets in a water phase under high-speed stirring at the rotating speed of 8000r/min, and controlling the diameter of the oil phase droplets to be between 5 and 60um through stirring and dispersing;
4) dropping the prepared suspension liquid with uniform dispersion and qualified particle size into a polymerization reaction kettle, introducing nitrogen for protection, starting a stirring device, setting the pressure to be 0.4-0.6MPa, slowly heating to 70 ℃, and starting free radical polymerization reaction for 12 hours;
5) and (3) carrying out suction filtration on the prepared high molecular polymer, washing for 2-3 times by using deionized water, drying in a vacuum oven, and finally crushing and sieving to prepare the physical expansion high molecular foaming agent.
Example 3
1) Preparation of oil phase mixture
Mixing 78 parts by mass of methyl methacrylate, 17 parts by mass of acrylonitrile, 4.5 parts by mass of methacrylonitrile, 0.5 part by mass of styrene, 0.3 part by mass of ethylene glycol dimethacrylate and 0.1 part by mass of glycerol dimethacrylate to form a shell raw material part of the high-molecular foaming agent; sequentially adding 20 parts by mass of petroleum ether, 17 parts by mass of isobutane, 0.4 part by mass of lauroyl peroxide and 0.4 part by mass of azodiisobutyronitrile to form a core raw material part of the high-molecular foaming agent, and uniformly mixing all the materials to prepare an oil phase mixture;
2) preparation of aqueous mixtures
Fully dissolving and uniformly mixing 200 parts by mass of deionized water, 100.2 parts by mass of non-surfactant nonylphenol polyoxyethylene ether TX-100.2 parts by mass, 0.2 part by mass of tween, 9 parts by mass of nano calcium hydroxide, 0.3 part by mass of methyl cellulose and 70 parts by mass of magnesium chloride to prepare an aqueous phase mixture;
3) putting the prepared oil phase mixture and the prepared water phase mixture into a high-speed dispersing agent, uniformly dispersing oil phase liquid drops into a water phase under high-speed stirring at the rotating speed of 6500r/min, and controlling the diameter of the oil phase liquid drops to be between 5 and 60um through stirring and dispersing;
4) dropping the prepared suspension liquid with uniform dispersion and qualified particle size into a polymerization reaction kettle, introducing nitrogen for protection, starting a stirring device, setting the pressure to be 0.4-0.6MPa, slowly heating to 65 ℃, and starting a free radical polymerization reaction, wherein the reaction time is 16 h;
5) and (3) carrying out suction filtration on the prepared high molecular polymer, washing for 2-3 times by using deionized water, drying in a vacuum oven, and finally crushing and sieving to prepare the physical expansion high molecular foaming agent.
The macromolecular foaming agent prepared by the invention has the advantages of complete core-shell structure, uniform particle size distribution, high foaming agent coating efficiency and good shell polymer heat resistance.
The high-molecular foaming agent prepared by the invention is light in weight, has a uniform and controllable closed pore structure, and solves the problems of nonuniform pore diameters, uncontrollable gas diffusion and the like generated in the foaming process of the material.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the physical thermal expansion high polymer foaming agent is characterized by comprising the following steps:
1) preparation of oil phase mixture: mixing 90-110 parts by mass of polymerized monomer, 20-40 parts by mass of inert hydrocarbon, 0.1-2.0 parts by mass of initiator and 0.01-1.0 part by mass of cross-linking agent to prepare an oil phase mixture;
2) preparation of aqueous phase mixture: mixing 10-15 parts by mass of a dispersing agent, 0.02-3.0 parts by mass of a stabilizer, 60-100 parts by mass of a polymerization inhibitor and 200-300 parts by mass of deionized water to prepare a water phase mixture;
3) mixing the oil phase mixture and the water phase mixture, and then shearing and stirring at a high speed, wherein the rotating speed is 4000-;
4) suspension polymerization: the reaction temperature is 50-100 ℃, the pressure is 0.1-2.0MPa, and the reaction time is 10-25 h;
5) and (4) carrying out suction filtration, washing and drying to obtain the physical expansion high polymer foaming agent. Is prepared by a suspension polymerization method.
2. The method for preparing a physical thermal expansion high molecular foaming agent according to claim 1, wherein the polymerization monomer is one or more of acrylonitrile, methacrylonitrile, vinylidene chloride, methyl methacrylate, butyl methacrylate, styrene, acrylic acid, methacrylic acid, hydroxypropyl methacrylate and N, N-dimethylacrylamide.
3. The method for preparing the physical thermal expansion high molecular foaming agent according to claim 1, wherein the inert hydrocarbon is one or more of isobutane, n-hexane, isopentane, n-pentane, neopentane, isooctane, heptane and petroleum ether.
4. The method for preparing a physically thermally expansive polymeric foaming agent according to claim 1, wherein the crosslinking agent is one or more of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerol diacrylate, glycerol dimethacrylate, PEG200 dimethacrylate, PEG400 dimethacrylate, PEG600 dimethacrylate, trimethylolpropane triacrylate, divinyl ether, 1, 4-butanediol divinyl ether, and divinylbenzene.
5. The method for preparing a physically thermally expansive polymeric blowing agent as claimed in claim 1, wherein said initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, t-butyl peroxybenzoate, t-butyl hydroperoxide, diacyl peroxide, methyl ethyl ketone peroxide, benzoyl peroxide, lauroyl peroxide, di- (2-ethylhexyl) peroxydicarbonate.
6. The method for preparing a physical thermal expansion polymeric blowing agent according to claim 1, wherein the dispersant is an inorganic dispersant and/or a water-soluble organic dispersant, wherein the inorganic dispersant is selected from hydroxides and oxides of magnesium, calcium, barium, iron, zinc, and manganese; the water soluble dispersant is selected from polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose, hydroxypropyl methylcellulose, carboxymethyl cellulose, silicon dioxide, agar powder, etc. Preferably one or more of nano magnesium hydroxide, nano calcium hydroxide, nano silicon dioxide, polyvinyl alcohol and methyl cellulose.
7. The method for preparing a physical thermal expansion high molecular foaming agent according to claim 1, wherein the stabilizer is a surfactant selected from one or more of alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ethers, tween, sodium dodecyl sulfate and sodium dodecyl sulfate.
8. The method for preparing a physical thermal expansion high molecular foaming agent according to claim 1, wherein the polymerization inhibitor is one or more of sodium chloride, potassium chloride, magnesium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, ammonium chloride, ammonium sulfate, sodium carbonate and potassium carbonate.
9. The method for preparing a physically thermally expansive polymeric blowing agent as claimed in claim 1, wherein the suspension polymerization reaction is carried out at a temperature of 60-80 ℃ under a pressure of 0.4-0.6MPa for a period of 15-20 hours.
10. The method for preparing a physical thermal expansion polymer foaming agent according to claim 1, wherein the amount of the inert hydrocarbon added to the oil phase mixture is 10 to 50% of the total mass of the polymerized monomers, the amount of the initiator added to the oil phase mixture is 0.01 to 3% of the total mass of the polymerized monomers, and the amount of the cross-linking agent added to the oil phase mixture is 0.01 to 2% of the total mass of the polymerized monomers;
in the water phase mixture, the addition amount of the stabilizer is 0.01-1% of the total mass of the deionized water, the addition amount of the dispersant is 1-10% of the total mass of the deionized water, and the addition amount of the polymerization inhibitor is 10-45% of the total mass of the deionized water.
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