CN115181384B - High-strength high-toughness polyacrylic imide foam material and preparation method and application thereof - Google Patents

High-strength high-toughness polyacrylic imide foam material and preparation method and application thereof Download PDF

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CN115181384B
CN115181384B CN202210840657.3A CN202210840657A CN115181384B CN 115181384 B CN115181384 B CN 115181384B CN 202210840657 A CN202210840657 A CN 202210840657A CN 115181384 B CN115181384 B CN 115181384B
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foam
hours
temperature
foaming
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CN115181384A (en
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胡爱军
杨士勇
李克迪
史亚伟
王志媛
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Cashem Advanced Materials Hi Tech Co ltd Zhejiang
Institute of Chemistry CAS
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Cashem Advanced Materials Hi Tech Co ltd Zhejiang
Institute of Chemistry CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—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 organic
    • C08J9/142—Compounds containing oxygen but no halogen atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention discloses a high-strength high-toughness polyacrylic imide foam material, and a preparation method and application thereof. The high-strength high-toughness polyacrylic imide foam material is prepared from the following raw materials in parts by mass: 50 parts of acrylic monomer containing carboxyl; 1-100 parts of nitrile group-containing acrylonitrile monomer; 0.1-50 parts of initiator; 0.1-50 parts of foaming agent; 0.1-50 parts of nucleating agent; 1-50 parts of prefoaming particles; wherein the prefoaming particles are prepared from the components in parts by mass. The preparation method comprises the following steps: mixing acrylic monomer containing carboxyl, acrylonitrile monomer containing nitrile group, initiator, foaming agent, nucleating agent and pre-foaming particles in proportion to obtain a mixture; then, carrying out polymerization reaction under a closed condition to obtain a polyacrylic imide foam prepolymer copolymer; and then continuously heating and foaming to obtain the high-strength high-toughness polyacrylic imide foam material. The invention adopts the prefoaming particles of the same material system as the PMI foam continuous phase to realize the purposes of homogeneous polymerization and toughening.

Description

High-strength high-toughness polyacrylic imide foam material and preparation method and application thereof
Technical Field
The invention belongs to the technology of polyacrylic imide foam materials, and relates to a high-strength high-toughness polyacrylic imide foam material, a preparation method and application thereof.
Background
The polypropylene imide (PMI) foams were first shown in Germany in the 60 s of the 20 th century. Compared with other foam materials, the PMI foam has the excellent characteristics of high strength, high modulus, isotropy, high temperature resistance, 100% closed pore, easy processing, heat setting and the like, and is a structural foam core material with optimal comprehensive performance at present. Currently, PMI foam is the preferred foam core material of a high-performance carbon fiber sandwich composite material, and the carbon fiber/PMI sandwich composite material is widely applied to bearing or secondary bearing structures of components.
The high modulus of Polymethacrylimide (PMI) materials and low elongation at break are also a feature. There has been no break in the toughening studies thereof. Japanese patent JP52-63989, JP59-42017 report on the modification of PMI materials with polybutadiene grafted rubber and polyolefin rubber in succession, which method deteriorates the thermal stability of the materials, loses the heat resistance thereof, and makes the thermal properties of the PMI materials not well maintained; in order to reduce the loss of thermal performance, the US4902742 patent adopts polysiloxane rubber to toughen and modify the PMI material, and discovers that the melt index of the resin is obviously improved while the impact strength is improved, and all the researches clearly show that the PMI resin system lacks toughness.
The PMI foam takes PMI resin as a matrix, and the low elongation at break of the PMI foam also limits the use stability of the material. In order to improve the use safety in aviation and transportation equipment, toughening research of PMI foam materials is increasingly paid attention to. EP356714 and JP2006045532 report the use of metal salts to form crosslinks of ionic structure in order to improve the mechanical stability of PMI foams, but there are likewise cases where the elongation at break is low. EP532023 invention employs a non-crosslinked, fine-cell structure to increase elongation at break, resulting in deterioration of heat resistance and creep properties. EP1678244 discloses that the elongation at break of the fine-pored foam obtained by changing the blowing agent or adding the insoluble nucleating agent in the presence of a crosslinking agent can reach 5.5%. However, because of the insoluble nucleating agent, a dust-proof agent is required to be added, the cost is increased, and the elongation at break of the foam with small cells is not more than 5.5%. The method for solving the problem of insufficient elongation at break provided by the ROHACELL FX product adopts a method for increasing the water absorption to improve the plasticizing effect of the product, and the high water content obviously damages the mechanical property and the thermodynamic property of the PMI foam. Patent CN100420702 describes PMI foams based on acrylonitrile, while giving materials with good tensile strength, their thermodynamic properties are slightly reduced. The patent US2013/0108817A1 adopts polyethylene glycol containing methacrylic acid alkane ester unsaturated end group as a cross-linking agent, which can reduce cracking of the PMI foam, especially in the temperature range of-60 ℃ to 200 ℃, and can greatly reduce cracking, and meanwhile, the PMI foam has extremely high ultimate tensile strength, the material breaking elongation can exceed 6.0%, and some even exceeds 9.0% while obtaining good heat resistance.
From the above researches, it can be found that the thermoplastic rubber or plastic toughening PMI material system is adopted, so that the heat resistance of the material is often influenced, and even the strength and modulus of the material are lost.
Disclosure of Invention
The invention aims to provide a high-strength high-toughness polypropylene imide foam material, and a preparation method and application thereof.
The invention adopts the prefoaming particles of the same material system as the PMI foam continuous phase, realizes the purposes of homogeneous polymerization and toughening through the regulation and control of prefoaming density, and can improve the elongation at break of the material without sacrificing the mechanical property and the thermal property of the material.
The invention provides a high-strength high-toughness polypropylene imide foam material which is prepared from the following raw materials in parts by mass:
wherein the prefoaming particles comprise the following components in parts by mass: 50 parts of the acrylic monomer containing carboxyl; 1-100 parts of nitrile group-containing acrylonitrile monomer; 0.1-50 parts of initiator; 0.1-50 parts of foaming agent; 0.1 to 50 parts of nucleating agent.
In the invention, the high-strength high-toughness polypropylene imide foam material is specifically prepared from the following raw materials in parts by mass in any one of 1-7:
1. 50 parts of acrylic monomer containing carboxyl; 50 parts of nitrile group-containing acrylonitrile monomer; 10 parts of an initiator; 25 parts of a foaming agent; 3 parts of nucleating agent; 15 parts of prefoaming particles;
2. 45 parts of acrylic monomer containing carboxyl; 55 parts of nitrile group-containing acrylonitrile monomer; 8 parts of an initiator; 20 parts of a foaming agent; 8 parts of nucleating agent; 10 parts of prefoaming particles;
3. 50 parts of acrylic monomer containing carboxyl; 50 parts of nitrile group-containing acrylonitrile monomer; 15 parts of an initiator; 25 parts of a foaming agent; 7 parts of nucleating agent; 10 parts of prefoaming particles;
4. 45 parts of acrylic monomer containing carboxyl; 55 parts of nitrile group-containing acrylonitrile monomer; 10 parts of an initiator; 18 parts of a foaming agent; 7 parts of nucleating agent; 35 parts of prefoaming particles;
5. 50 parts of acrylic monomer containing carboxyl; 50 parts of nitrile group-containing acrylonitrile monomer; 7 parts of an initiator; 18 parts of a foaming agent; 5 parts of nucleating agent; 15 parts of prefoaming particles;
6. 45 parts of acrylic monomer containing carboxyl; 60 parts of nitrile group-containing acrylonitrile monomer; 10 parts of an initiator; 25 parts of a foaming agent; 10 parts of nucleating agent; 25 parts of prefoaming particles;
7. 60 parts of acrylic monomer containing carboxyl; 40 parts of nitrile group-containing acrylonitrile monomer; 10 parts of an initiator; 20 parts of a foaming agent; 8 parts of nucleating agent; 5 parts of prefoamed particles.
In the above material, the carboxyl group-containing acrylic monomer is selected from methacrylic acid and/or acrylic acid;
the nitrile group-containing acrylonitrile monomer is selected from methacrylonitrile and/or acrylonitrile.
In the above materials, the initiator is at least one selected from tert-amyl peroxyacetate (taca for short), benzoyl peroxide (BPO for short), tert-butyl peroxy2-ethylhexanoate (TBPO for short), tert-amyl peroxybenzoate (TAPB for short), tert-butyl peroxybenzoate (TBPB for short), azobisisobutyronitrile (AIBN for short) and azoiso Ding Qingji formamide (CABN for short);
the foaming agent is at least one selected from ethanol, propanol, isopropanol, water, tertiary butanol and amyl alcohol;
the nucleating agent is at least one selected from the group consisting of carbonamide, formamide, N-methylformamide and N, N-dimethylformamide.
In the above material, the preparation method of the prefoamed particle comprises the following steps:
1) Mixing the acrylic monomer containing carboxyl, the acrylonitrile monomer containing nitrile group, an initiator, a foaming agent and a nucleating agent according to a proportion to obtain a mixed solution;
2) Standing and polymerizing the mixed solution obtained in the step 1) under a sealing condition to obtain a polyacrylic imide prepolymer;
3) Crushing the polyacrylic imide prepolymer obtained in the step 2), dissolving the crushed polyacrylic imide prepolymer in an organic solvent, controlling the system concentration below 20%, and filtering to obtain a prepolymer solution;
4) Precipitating the prepolymer solution obtained in the step 3) by adopting a low-boiling-point alcohol solvent, and drying to obtain solid powder;
5) Heating the solid powder obtained in the step 4), and crushing to obtain the prefoamed particles.
Steps 3) to 4) are employed in the process of the invention to obtain soluble, high molecular weight prepolymers and with a certain purification effect.
In the material step 2), the temperature of the static polymerization can be 35-80 ℃ and the time can be 48-120 hours;
the stationary polymerization is carried out in a sealable cavity mold.
In the material step 3), the organic solvent is at least one selected from N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, ethyl lactate, cyclopentanone, cyclohexanone, methyl ethyl ketone, ethyl acetate and butyl acetate;
in the step 4), the low boiling point alcohol solvent is at least one selected from methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tertiary butanol, 1-amyl alcohol, 2-amyl alcohol and 3-amyl alcohol;
the drying temperature can be 60-100 ℃;
in the step 5), the heating temperature of the solid powder can be 170-220 ℃ and the heating time can be 10-60 min;
the particle size of the prefoamed particles can be 1-30 mu m, and the density can be 0.8-1.1 g/cm 3 。
The invention also provides a preparation method of the material, which comprises the following steps: (1) Mixing the acrylic monomer containing carboxyl, the acrylonitrile monomer containing nitrile group, the initiator, the foaming agent, the nucleating agent and the pre-foaming particles in proportion to obtain a mixture;
(2) Carrying out polymerization reaction on the mixture under a closed condition to obtain a polyacrylic imide foam prepolymer copolymer;
(3) And heating and foaming the polyacrylic imide foam prepolymer copolymer to obtain the high-strength high-toughness polyacrylic imide foam material.
In the step (1) of the preparation method, the mixing is performed under stirring, and the mixing time can be 1-8 hours, specifically 3, 4, 4.5, 5 or 3-5 hours;
in the step (2), the temperature of the polymerization reaction can be 40-150 ℃ and the time can be 24-150 hours, the polymerization reaction is heated in a gradient heating mode, and the temperature is raised to a certain temperature and then the reaction is kept at a certain temperature;
further, the gradient heating mode is specifically as follows:
the reaction is carried out for 30 to 60 hours under the heat preservation of 40 to 60 ℃, then the reaction is carried out for 20 to 50 hours under the temperature rising from 40 to 60 ℃ to 80 to 90 ℃, and finally the reaction is carried out for 30 to 60 hours under the temperature rising from 80 to 90 ℃ to 100 to 140 ℃;
in the step (3), the temperature of the heated foaming may be 180 to 250 ℃, specifically 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃ or 190 to 230 ℃, and the time may be 1 to 10 hours, specifically 4, 4.5, 5, 6, 7 hours or 4 to 7 hours.
In the above preparation method step (2), the polymerization reaction is performed in the presence of an inert atmosphere including nitrogen and/or argon.
The invention further provides application of the high-strength high-toughness polypropylene imide foam material in preparing any one of the following materials:
a) A high temperature resistant structural sandwich material having a requirement for elongation at break of the foam material;
b) A high temperature resistant insulating material;
c) High temperature resistant sound insulating material;
d) A high temperature resistant wave-transparent material.
The invention has the following advantages:
the pre-foaming particles are adopted to toughen the poly (meth) acrylimide foam material, the toughening effect is achieved through the homogeneous polymerization of two identical material systems, and the elongation at break of the material can be improved without sacrificing the mechanical property and the thermal property of the material; meanwhile, the prefoamed particles have good compatibility with a material system, have small influence on the preparation process of the material, and can not change the density performance of the material.
Drawings
FIG. 1 SEM comparison of PMI foams before and after toughening modification of example 1 of the present invention; wherein figure (a) is the product before modification and figure 1 (b) is the product after modification.
FIG. 2 shows the compressive strength of PMI foams before and after toughening modification of inventive examples 1-2 and comparative examples 1-2.
FIG. 3 is a graph showing the tensile strength of PMI foams before and after toughening modification of examples 1-2 of the present invention and comparative examples 1-2.
FIG. 4 is a graph showing the comparison of the elongation at break of PMI foams before and after toughening modification in examples 1-2 and comparative examples 1-2 of the present invention
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
The preparation process of the polypropylene imide-based foam of the present invention is described below with reference to specific examples, and "parts" used in the examples are not specifically described and are denoted as "parts by weight".
The invention adopts the prefoaming particles of the same material system as the PMI foam continuous phase, realizes the purposes of homogeneous polymerization and toughening through the regulation and control of prefoaming density, and can improve the elongation at break of the material without sacrificing the mechanical property and the thermal property of the material.
The preparation method of the pre-sent particles of the polyacrylic imide in the following embodiment specifically comprises the following steps:
step one: uniformly mixing a certain amount of acrylic monomer containing carboxyl, acrylonitrile monomer containing nitrile group, initiator, foaming agent and nucleating agent at room temperature (25 ℃) to obtain uniform solution;
injecting the solution obtained in the first step into a glass tube, sealing, and standing and polymerizing at 35-80 ℃ for 48-120 hours to obtain a uniform polyacrylamide prepolymer;
step three: crushing the prepolymer obtained in the second step, dissolving the crushed prepolymer in organic solvents such as dimethylacetamide and the like, controlling the concentration below 20%, and filtering to obtain a uniform solution;
step four: precipitating the solution obtained in the step three by adopting solvents such as ethanol and the like, and drying at 60-100 ℃ to obtain solid powder;
step five: heating the solid obtained in the fourth step at 170-220 ℃ for 10-60 min, and crushing to obtain pre-developed particles (pre-developed particles for short) of the polyacrylic imide, wherein the particle size is 1-30 microns, and the density is 0.8-1.1 g/cm 3 In the range, reserve.
Example 1
The preparation method of the pre-sent particles of the polyacrylic imide specifically comprises the following steps:
step one: 50 parts of methacrylic acid, 50 parts of methacrylonitrile, 2 parts of AIBN, 8 parts of TBPO, 3 parts of formamide and 25 parts of amyl alcohol are uniformly mixed at room temperature (25 ℃) to obtain a uniform solution;
injecting the solution obtained in the first step into a glass tube, sealing, and standing and polymerizing for 100 hours at 50 ℃ to obtain a uniform polyacrylamide prepolymer;
step three: crushing the prepolymer obtained in the second step, dissolving the crushed prepolymer in organic solvents such as dimethylacetamide and the like, controlling the concentration below 20%, and filtering to obtain a uniform solution;
step four: precipitating the solution obtained in the third step by adopting solvents such as ethanol and the like, and drying at 90 ℃ to obtain solid powder;
step five: heating the solid obtained in the fourth step at 200deg.C for 45min, pulverizing to obtain pre-developed particles (pre-developed particles for short), and controlling particle diameterIs 8-20 micrometers and has a density of 0.9-1.0 g/cm 3 In the range, reserve.
Preparation of high-strength high-toughness polyacrylic imide foam materials:
1) Sequentially adding 50 parts of methacrylic acid, 50 parts of methacrylonitrile, 15 parts of prefoamed particles, 2 parts of AIBN, 8 parts of TBPO, 3 parts of formamide and 25 parts of amyl alcohol into a three-necked glass flask, and stirring for 4 hours at room temperature (25 ℃ and the same below) under the protection of nitrogen to form a homogeneous solution;
2) The homogeneous solution was transferred to a mold consisting of 2 glass plates and a sealant frame and polymerized under the following conditions: the reaction is carried out for 50 hours at the temperature of 60 ℃, then the reaction is carried out for 30 hours from the temperature of 60 ℃ to the temperature of 90 ℃, and finally the reaction is carried out for 50 hours from the temperature of 90 ℃ to the temperature of 130 ℃ to obtain the foam prepolymer copolymer resin board;
3) Foaming the obtained foam prepolymer copolymer resin plate at 200 ℃ for 5 hours to obtain a polypropylene imide foam plate blank;
the obtained polypropylene imide foam board blank is mechanically processed to obtain polypropylene imide foam material with the density of 110kg/m 3 The foam cells are uniform, the deformation amount at 180 ℃/0.5MPa/2h is 0.3%, the compressive strength is 3.0MPa, the tensile strength is 3.6MPa, the modulus is 180MPa, and the elongation at break is 5.1%.
As shown in the SEM results of FIG. 1, the microstructure of the polyimide foam material of the invention is not changed obviously, and the elongation at break is improved obviously.
Example 2
The prefoamed particles were prepared according to the method of example 1 of the present invention, except that the raw materials used in step one were as follows: 45 parts of methacrylic acid, 55 parts of methacrylonitrile, 8 parts of TBPO, 8 parts of formamide and 20 parts of isopropanol.
Sequentially adding 45 parts of methacrylic acid, 55 parts of methacrylonitrile, 10 parts of prefoamed particles, 8 parts of TBPO, 8 parts of formamide and 20 parts of isopropanol into a three-necked glass flask, and stirring at room temperature for 4 hours under the protection of nitrogen to form a homogeneous solution;
the homogeneous solution was transferred to a mold consisting of 2 glass plates and a sealant frame and polymerized under the following conditions: the reaction is carried out for 50 hours at the temperature of 60 ℃, then the reaction is carried out for 30 hours from the temperature of 60 ℃ to the temperature of 90 ℃, and finally the reaction is carried out for 50 hours from the temperature of 90 ℃ to the temperature of 120 ℃ to obtain the foam prepolymer copolymer resin board;
foaming the obtained foam prepolymer copolymer resin plate at 210 ℃ for 4.5 hours to obtain a polypropylene imide foam plate blank;
the obtained polypropylene imide foam board blank is mechanically processed to obtain polypropylene imide foam material with the density of 108kg/m 3 The foam cells are uniform, the deformation amount at 180 ℃/0.5MPa/2h is 0.32%, the compressive strength is 2.9MPa, the tensile strength is 3.5MPa, the modulus is 180MPa, and the elongation at break is 5.2%.
Comparative example 1
Sequentially adding 50 parts of methacrylic acid, 50 parts of methacrylonitrile, 2 parts of AIBN, 8 parts of TBPO, 3 parts of formamide and 25 parts of amyl alcohol into a three-necked glass flask, and stirring for 4 hours at room temperature under the protection of nitrogen to form a homogeneous solution;
the homogeneous solution was transferred to a mold consisting of 2 glass plates and a sealant frame and polymerized under the following conditions: the reaction is carried out for 50 hours at the temperature of 60 ℃, then the reaction is carried out for 30 hours from the temperature of 60 ℃ to the temperature of 90 ℃, and finally the reaction is carried out for 50 hours from the temperature of 90 ℃ to the temperature of 130 ℃ to obtain the foam prepolymer copolymer resin board;
foaming the obtained foam prepolymer copolymer resin plate at 200 ℃ for 5 hours to obtain a polypropylene imide foam plate blank;
the obtained polypropylene imide foam board blank is mechanically processed to obtain polypropylene imide foam material with the density of 110kg/m 3 The foam cells are uniform, the deformation amount at 180 ℃/0.5MPa/2h is 0.3%, the compressive strength is 3.1MPa, the tensile strength is 3.6MPa, the modulus is 180MPa, and the elongation at break is 2.8%.
Comparative example 2
Sequentially adding 45 parts of methacrylic acid, 55 parts of methacrylonitrile, 8 parts of TBPO, 8 parts of formamide and 20 parts of isopropanol into a three-necked glass flask, and stirring at room temperature for 4 hours under the protection of nitrogen to form a homogeneous solution;
the homogeneous solution was transferred to a mold consisting of 2 glass plates and a sealant frame and polymerized under the following conditions: the reaction is carried out for 50 hours at the temperature of 60 ℃, then the reaction is carried out for 30 hours from the temperature of 60 ℃ to the temperature of 90 ℃, and finally the reaction is carried out for 50 hours from the temperature of 90 ℃ to the temperature of 120 ℃ to obtain the foam prepolymer copolymer resin board;
foaming the obtained foam prepolymer copolymer resin plate at 210 ℃ for 4.5 hours to obtain a polypropylene imide foam plate blank;
the obtained polypropylene imide foam board blank is mechanically processed to obtain polypropylene imide foam material with the density of 108kg/m 3 The foam cells are uniform, the deformation amount at 180 ℃/0.5MPa/2h is 0.32%, the compressive strength is 3.0MPa, the tensile strength is 3.5MPa, the modulus is 180MPa, and the elongation at break is 2.8%.
As can be seen from the above experiments in combination with the results of FIGS. 2 to 4, the density of the polypropylene imide foam sheet material blank in example 1 of the present invention was 110kg/m 3 Elongation at break of 5.1% and at the same density as in comparative example 1, elongation at break was only 2.8%; the density of the polypropylene imide foam sheet blank in example 2 of the present invention was 108kg/m 3 Elongation at break was 5.2%, whereas at the same density as in comparative example 2, elongation at break was only 2.8%. Thus, comparison of the data in example 1 and comparative example 1, and example 2 and comparative example 2, respectively, shows that the pre-expanded particles of the same material system as the PMI foam continuous phase are adopted in the invention, and the obtained polyimide foam material has better toughness.
Example 3
The prefoamed particles were prepared according to the method of example 1 of the present invention, except that the raw materials used in step one were as follows: 50 parts of methacrylic acid, 50 parts of acrylonitrile, 7 parts of CABN, 8 parts of TAPB, 5 parts of formamide, 2 parts of carbonamide, 20 parts of tert-butanol and 5 parts of water.
50 parts of methacrylic acid, 50 parts of acrylonitrile, 10 parts of prefoaming particles, 7 parts of CABN, 8 parts of TAPB, 5 parts of formamide, 2 parts of carbonamide, 20 parts of tertiary butanol and 5 parts of water are sequentially added into a three-port glass flask, and the mixture is stirred for 4 hours at room temperature under the protection of nitrogen to form a homogeneous solution;
the homogeneous solution was transferred to a mold consisting of 2 glass plates and a sealant frame and polymerized under the following conditions: the reaction is carried out for 55 hours at the temperature of 60 ℃, then the reaction is carried out for 20 hours from the temperature of 60 ℃ to 80 ℃, and finally the reaction is carried out for 40 hours from the temperature of 80 ℃ to 100 ℃ to obtain the foam prepolymer copolymer resin plate;
foaming the obtained foam prepolymer copolymer resin plate at 220 ℃ for 5 hours to obtain a polyacrylic imide foam plate blank;
the obtained polypropylene imide foam board blank is mechanically processed to obtain polypropylene imide foam material with the density of 75kg/m 3 The foam cells are uniform, the deformation amount at 150 ℃/0.5MPa/2h is 0.5%, the compressive strength is 1.7MPa, the tensile strength is 2.2MPa, the modulus is 180MPa, and the elongation at break is 5.5%.
Example 4
The prefoamed particles were prepared according to the method of example 1 of the present invention, except that the raw materials used in step one were as follows: 45 parts of methacrylic acid, 55 parts of acrylonitrile, 10 parts of TAPB, 5 parts of formamide, 2 parts of carbonamide, 15 parts of tertiary butanol and 3 parts of water.
45 parts of methacrylic acid, 55 parts of acrylonitrile, 35 parts of prefoaming particles, 10 parts of TAPB, 5 parts of formamide, 2 parts of carbonamide, 15 parts of tertiary butanol and 3 parts of water are sequentially added into a three-neck glass flask, and stirred for 5 hours at room temperature under the protection of nitrogen to form a homogeneous solution;
the homogeneous solution was transferred to a mold consisting of 2 glass plates and a sealant frame and polymerized under the following conditions: the reaction is carried out for 60 hours at the temperature of 50 ℃, then the reaction is carried out for 20 hours at the temperature of 90 ℃ from 50 ℃, and finally the reaction is carried out for 60 hours at the temperature of 120 ℃ from 90 ℃ to obtain a foam prepolymer copolymer resin plate;
foaming the obtained foam prepolymer copolymer resin plate at 230 ℃ for 4 hours to obtain a polyacrylic imide foam plate blank;
the obtained polyacrylic imide foam board is subjected to the process ofThe blank is mechanically processed to obtain a polyacrylic imide foam material with the density of 80kg/m 3 The foam cells are uniform, the deformation amount at 150 ℃/0.5MPa/2h is 0.3%, the compressive strength is 1.8MPa, the tensile strength is 2.5MPa, the modulus is 180MPa, and the elongation at break is 5.5%.
Example 5
The prefoamed particles were prepared according to the method of example 1 of the present invention, except that the raw materials used in step one were as follows: 50 parts of methacrylic acid, 50 parts of methacrylonitrile, 5 parts of TAPB, 2 parts of BPO, 3 parts of formamide, 2 parts of N-methylformamide, 15 parts of tert-butanol and 3 parts of water.
50 parts of methacrylic acid, 50 parts of methacrylonitrile, 15 parts of prefoaming particles, 5 parts of TAPB, 2 parts of BPO, 3 parts of formamide, 2 parts of N-methylformamide, 15 parts of tertiary butanol and 3 parts of water are sequentially added into a three-necked glass flask, and stirred for 5 hours at room temperature under the protection of nitrogen to form a homogeneous solution;
the homogeneous solution was transferred to a mold consisting of 2 glass plates and a sealant frame and polymerized under the following conditions: the reaction is carried out for 60 hours at the temperature of 60 ℃, then the reaction is carried out for 20 hours at the temperature of 90 ℃ from 60 ℃, and finally the reaction is carried out for 60 hours at the temperature of 140 ℃ from 90 ℃ to obtain a foam prepolymer copolymer resin plate;
foaming the obtained foam prepolymer copolymer resin plate at 190 ℃ for 7 hours to obtain a polyacrylic imide foam plate blank;
the obtained polypropylene imide foam board blank is mechanically processed to obtain polypropylene imide foam material with the density of 200kg/m 3 The foam cells are uniform, the deformation amount at 180 ℃/0.5MPa/2h is 0.1%, the compressive strength is 7.1MPa, the tensile strength is 12.2MPa, the modulus is 280MPa, and the elongation at break is 6.5%.
Example 6
The prefoamed particles were prepared according to the method of example 1 of the present invention, except that the raw materials used in step one were as follows: 45 parts of methacrylic acid, 60 parts of methacrylonitrile, 5 parts of TBPB, 5 parts of BPO, 10 parts of formamide and 25 parts of propanol.
45 parts of methacrylic acid, 60 parts of methacrylonitrile, 25 parts of prefoamed particles, 5 parts of TBPB, 5 parts of BPO, 10 parts of formamide and 25 parts of propanol are sequentially added into a three-necked glass flask, and stirred for 3 hours at room temperature under the protection of nitrogen to form a homogeneous solution;
the homogeneous solution was transferred to a mold consisting of 2 glass plates and a sealant frame and polymerized under the following conditions: the reaction is carried out for 30 hours at the temperature of 40 ℃, then the reaction is carried out for 50 hours from the temperature of 40 ℃ to the temperature of 90 ℃, and finally the reaction is carried out for 50 hours from the temperature of 90 ℃ to the temperature of 110 ℃ to obtain the foam prepolymer copolymer resin board;
foaming the obtained foam prepolymer copolymer resin plate at 200 ℃ for 5 hours to obtain a polypropylene imide foam plate blank;
the obtained polypropylene imide foam board blank is mechanically processed to obtain polypropylene imide foam material with the density of 150kg/m 3 The foam cells are uniform, the deformation amount at 180 ℃/0.5MPa/2h is 0.2%, the compressive strength is 4.1MPa, the tensile strength is 5.1MPa, the modulus is 190MPa, and the elongation at break is 5.5%.
Example 7
The prefoamed particles were prepared according to the method of example 1 of the present invention, except that the raw materials used in step one were as follows: 60 parts of methacrylic acid, 40 parts of methacrylonitrile, 5 parts of AIBN, 5 parts of TAPB, 8 parts of formamide and 20 parts of isopropanol.
60 parts of methacrylic acid, 40 parts of methacrylonitrile, 5 parts of prefoamed particles, 5 parts of AIBN, 5 parts of TAPB, 8 parts of formamide and 20 parts of isopropanol are sequentially added into a three-necked glass flask, and stirred for 4.5 hours at room temperature under the protection of nitrogen to form a homogeneous solution;
the homogeneous solution was transferred to a mold consisting of 2 glass plates and a sealant frame and polymerized under the following conditions: the reaction is carried out for 40 hours at 50 ℃, then the reaction is carried out for 20 hours from the temperature of 50 ℃ to 70 ℃, then the reaction is carried out for 20 hours from the temperature of 70 ℃ to 80 ℃, and finally the reaction is carried out for 30 hours from the temperature of 80 ℃ to 110 ℃ to obtain the foam prepolymer copolymer resin board;
foaming the obtained foam prepolymer copolymer resin plate at 210 ℃ for 4.5 hours to obtain a polypropylene imide foam plate blank;
the obtained polypropylene imide foam board blank is mechanically processed to obtain polypropylene imide foam material with the density of 115kg/m 3 The foam cells are uniform, the deformation amount at 180 ℃/0.3MPa/2h is 0.24%, the compressive strength is 3.6MPa, the tensile strength is 3.6MPa, the modulus is 190MPa, and the elongation at break is 5.5%.
Example 8
The densities obtained by the preparation of examples 1, 2, 3, 4, 5, 6 and 7 were 110kg/m, respectively 3 、108kg/m 3 、75kg/m 3 、80kg/m 3 、200kg/m 3 、150kg/m 3 、115kg/m 3 PMI foam is mechanically processed into foam boards with required sizes, fiber (or cloth)/AG 80 epoxy prepreg (0 degree/90 degree/0 degree/90 degree) is respectively paved on the surfaces of the foam boards, and the PMI sandwich composite material is prepared by limiting, solidifying and forming by a press, wherein the solidifying process is 180 ℃/0.3MPa/2 h. The material is suitable for the field of light high-strength composite materials. PMI foams with different densities can be used for preparing PMI sandwich composite materials with different intensities. In general, the higher the PMI density, the higher the strength of the PMI sandwich composite material.
In conclusion, the PMI foam has excellent heat resistance and mechanical properties, and also has low dielectric constant and low thermal conductivity, so that the PMI foam has wide application prospect in the fields of structural function integration such as high-temperature-resistant wave transmission and heat insulation.
The embodiment of the invention provides a preparation method of a high-strength and high-toughness polyacrylic imide foam material, the prepared polyacrylic imide foam material adopts the prefoaming particles, the prepared PMI foam has the characteristics of high closed porosity, good high temperature resistance, high compression strength and the like, and the density of the prepared foam is 50 to the whole250kg/m 3 The closed pore rate is more than 90 percent, and the thermal deformation temperature is not less than 200 ℃. For example, a density of 110kg/m at room temperature 3 The compressive strength of the foam is not less than 2.5MPa; the polyimide foam sheet prepared in example 1 of the present invention had a density of 110kg/m at 180℃and a pressure of 0.5MPa 3 The foam of (2) has a compression set of less than 1% after 2 hours of processing.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.

Claims (10)

1. The high-strength high-toughness polypropylene imide foam material is characterized by comprising the following raw materials in parts by mass:
wherein the prefoaming particles comprise the following components in parts by mass: 50 parts of the acrylic monomer containing carboxyl; 1-100 parts of nitrile group-containing acrylonitrile monomer; 0.1-50 parts of initiator; 0.1-50 parts of foaming agent; 0.1 to 50 parts of nucleating agent.
2. A material according to claim 1, characterized in that: the acrylic monomer containing carboxyl is selected from methacrylic acid and/or acrylic acid;
the nitrile group-containing acrylonitrile monomer is selected from methacrylonitrile and/or acrylonitrile.
3. A material according to claim 1, characterized in that: the initiator is at least one selected from tertiary amyl peroxyacetate, benzoyl peroxide, tertiary butyl peroxy-2-ethylhexanoate, tertiary amyl peroxybenzoate, tertiary butyl peroxybenzoate, azobisisobutyronitrile and azoiso Ding Qingji formamide;
the foaming agent is at least one selected from ethanol, propanol, isopropanol, water, tertiary butanol and amyl alcohol;
the nucleating agent is at least one selected from the group consisting of carbonamide, formamide, N-methylformamide and N, N-dimethylformamide.
4. A material according to any one of claims 1-3, characterized in that: the preparation method of the prefoamed particle comprises the following steps:
1) Mixing the acrylic monomer containing carboxyl, the acrylonitrile monomer containing nitrile group, an initiator, a foaming agent and a nucleating agent according to a proportion to obtain a mixed solution;
2) Standing and polymerizing the mixed solution obtained in the step 1) under a sealing condition to obtain a polyacrylic imide prepolymer;
3) Crushing the polyacrylic imide prepolymer obtained in the step 2), dissolving the crushed polyacrylic imide prepolymer in an organic solvent, controlling the system concentration below 20%, and filtering to obtain a prepolymer solution;
4) Precipitating the prepolymer solution obtained in the step 3) by adopting a low-boiling-point alcohol solvent, and drying to obtain solid powder;
the low-boiling point alcohol solvent is at least one selected from methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tertiary butanol, 1-amyl alcohol, 2-amyl alcohol and 3-amyl alcohol;
5) Heating the solid powder obtained in the step 4), and crushing to obtain the prefoamed particles.
5. The material according to claim 4, wherein: in the step 2), the temperature of the static polymerization is 35-80 ℃ and the time is 48-120 hours;
the stationary polymerization is carried out in a sealable cavity mold.
6. The material according to claim 4, wherein: in the step 3), the organic solvent is at least one selected from N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, ethyl lactate, cyclopentanone, cyclohexanone, methyl ethyl ketone, ethyl acetate and butyl acetate;
in the step 4), the drying temperature is 60-100 ℃;
in the step 5), the heating temperature of the solid powder is 170-220 ℃ and the time is 10-60 min;
the particle diameter of the prefoamed particles is 1-30 mu m, and the density is 0.8-1.1 g/cm 3 。
7. A method of preparing a material as claimed in any one of claims 1 to 6, comprising the steps of: (1) Mixing the acrylic monomer containing carboxyl, the acrylonitrile monomer containing nitrile group, the initiator, the foaming agent, the nucleating agent and the pre-foaming particles in proportion to obtain a mixture;
(2) Carrying out polymerization reaction on the mixture under a closed condition to obtain a polyacrylic imide foam prepolymer copolymer;
(3) And heating and foaming the polyacrylic imide foam prepolymer copolymer to obtain the high-strength high-toughness polyacrylic imide foam material.
8. The method of manufacturing according to claim 7, wherein: in the step (1), the mixing is carried out under the stirring condition, and the mixing time is 1-8 hours;
in the step (2), the temperature of the polymerization reaction is 40-150 ℃ and the time is 24-150 hours; the polymerization reaction is heated in a gradient temperature raising mode, and then a heat preservation reaction is carried out;
in the step (3), the temperature of the heating foaming is 180-250 ℃ and the time is 1-10 hours.
9. The preparation method according to claim 7 or 8, characterized in that: in step (2), the polymerization is carried out in the presence of an inert atmosphere comprising nitrogen and/or argon.
10. Use of the high-strength high-toughness polyacrylamides foam material according to anyone of claims 1-6 for the preparation of anyone of the following a) -d):
a) High temperature resistant structural sandwich material with requirement on elongation at break of foam material
b) A high temperature resistant insulating material;
c) High temperature resistant sound insulating material;
d) A high temperature resistant wave-transparent material.
CN202210840657.3A 2022-07-18 2022-07-18 High-strength high-toughness polyacrylic imide foam material and preparation method and application thereof Active CN115181384B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5132371A (en) * 1988-12-13 1992-07-21 Mitsubishi Rayon Company Ltd. Methacrylimide-containing polymer and thermoplastic resin composition comprising this polymer
CN104945553A (en) * 2015-07-21 2015-09-30 江苏兆鋆新材料股份有限公司 Preparation method and application of high-tenacity foam material
CN106366232A (en) * 2016-09-19 2017-02-01 浙江中科恒泰新材料科技有限公司 Preparation method of microporous PMI (polymethacrylimide) foam and PMI foam prepared by method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5132371A (en) * 1988-12-13 1992-07-21 Mitsubishi Rayon Company Ltd. Methacrylimide-containing polymer and thermoplastic resin composition comprising this polymer
CN104945553A (en) * 2015-07-21 2015-09-30 江苏兆鋆新材料股份有限公司 Preparation method and application of high-tenacity foam material
CN106366232A (en) * 2016-09-19 2017-02-01 浙江中科恒泰新材料科技有限公司 Preparation method of microporous PMI (polymethacrylimide) foam and PMI foam prepared by method

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