CN115181384A - High-strength high-toughness polypropylene imide foam material and preparation method and application thereof - Google Patents
High-strength high-toughness polypropylene imide foam material and preparation method and application thereof Download PDFInfo
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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
- 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
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- 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
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
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- 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
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- 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
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- 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
Abstract
The invention discloses a high-strength high-toughness polypropylene imide foam material and a preparation method and application thereof. A high-strength high-toughness polypropylene imide foam material is prepared from the following raw materials in parts by mass: 50 parts of carboxyl-containing acrylic monomer; 1-100 parts of nitrile monomer containing nitrile group; 0.1-50 parts of an initiator; 0.1-50 parts of foaming agent; 0.1-50 parts of nucleating agent; 1-50 parts of pre-foaming particles; wherein the pre-foaming particles comprise the components in parts by mass. The preparation method comprises the following steps: mixing acrylic monomers containing carboxyl, acrylonitrile monomers containing nitrile groups, an initiator, a foaming agent, a nucleating agent and pre-foaming particles in proportion to obtain a mixture; then carrying out polymerization reaction under a closed condition to obtain a polypropylene imide foam prepolymer copolymer; and then continuously heating and foaming to obtain the high-strength high-toughness polypropylene imide foam material. The invention adopts pre-foaming particles of the same material system as the PMI foam continuous phase, and achieves the purposes of homogeneous polymerization and toughening.
Description
Technical Field
The invention belongs to the technology of polypropylene imide foam materials, and relates to a high-strength high-toughness polypropylene imide foam material as well as a preparation method and application thereof.
Background
Polyacrylimide (PMI) foams appeared at the earliest 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 cell, easy processing, heat setting and the like, and is a structural foam core material with the optimal comprehensive performance at present. At present, PMI foam is the first choice foam core material of a high-performance carbon fiber sandwich composite material, and the carbon fiber/PMI sandwich composite material is widely applied to a bearing or secondary bearing structure of a component.
The properties of Polymethacrylimide (PMI) material are high modulus and low elongation at break. Therefore, the research on toughening of the material has not been interrupted. Japanese patents JP52-63989, JP59-42017 successively report the modification of PMI materials with polybutadiene graft rubber and polyolefin rubber, which results in poor thermal stability of the materials, loss of heat resistance and failure to maintain good thermal properties of the PMI materials; to reduce the loss of thermal properties, the US4902742 patent uses polysiloxane rubber to toughen and modify PMI materials and found that the melt index of the resin was significantly increased while increasing impact strength, and these studies all indicate that the PMI resin system lacks toughness.
The PMI foam is based on PMI resin, 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, the toughening research of PMI foam materials is increasingly emphasized. EP356714, JP2006045532 report the use of metal salts to form crosslinks of ionic structures to improve the mechanical property stability of PMI foams, but also in the case of lower elongation at break. EP532023 invention uses a non-crosslinked, fine cell structure to increase elongation at break, resulting in poor heat resistance and creep properties. EP1678244 discloses fine-celled foams with elongation at break of up to 5.5% which are obtained by changing the blowing agent or adding insoluble nucleating agents in the presence of crosslinking agents. However, the use of insoluble nucleating agents requires the addition of dust-proofing agents, which increases the cost, and the elongation at break of small-cell foams does not exceed 5.5%. The method for solving the problem of insufficient elongation at break provided by the ROHACELL FX product is to improve the plasticizing effect of the product by adopting a method for increasing water absorption, and the mechanical property and the thermodynamic property of PMI foam are obviously damaged due to high water content. Patent CN100420702 describes acrylonitrile based PMI foams which, although giving the material good tensile strength, at the same time have a slight decrease in their thermodynamic properties. Patent US2013/0108817A1 uses polyethylene glycol containing an unsaturated end group of an alkyl methacrylate as a cross-linking agent, which can reduce the cracking of PMI foams, especially greatly reduce the cracking in the temperature range of-60 ℃ to 200 ℃, and simultaneously, while obtaining good heat resistance, make PMI foams have particularly high ultimate tensile strength, and the elongation at break of the material can exceed 6.0%, and some even exceed 9.0%.
From the above researches, it can be found that the thermoplastic rubber or plastic toughened PMI material system often affects the heat resistance of the material itself, and even causes loss of the strength and modulus of the material.
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 pre-foaming 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 the pre-foaming 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:
the pre-foaming particle comprises the following components in parts by mass: 50 parts of carboxyl-containing acrylic monomer; 1-100 parts of nitrile group-containing acrylonitrile monomer; 0.1-50 parts of an initiator; 0.1-50 parts of foaming agent; 0.1 to 50 portions of nucleating agent.
In the invention, the high-strength high-toughness polypropylene imide foam material is prepared from the following raw materials in any one of 1-7 by mass:
1. 50 parts of carboxyl-containing acrylic monomer; 50 parts of nitrile group-containing acrylonitrile monomer; 10 parts of an initiator; 25 parts of a foaming agent; 3 parts of a nucleating agent; 15 parts of pre-foaming particles;
2. 45 parts of carboxyl-containing acrylic monomer; 55 parts of nitrile group-containing acrylonitrile monomer; 8 parts of an initiator; 20 parts of foaming agent; 8 parts of a nucleating agent; 10 parts of pre-foaming particles;
3. 50 parts of carboxyl-containing acrylic monomer; 50 parts of nitrile group-containing acrylonitrile monomer; 15 parts of an initiator; 25 parts of a foaming agent; 7 parts of a nucleating agent; 10 parts of pre-foaming particles;
4. 45 parts of carboxyl-containing acrylic monomer; 55 parts of nitrile group-containing acrylonitrile monomer; 10 parts of an initiator; 18 parts of a foaming agent; 7 parts of a nucleating agent; 35 parts of pre-foaming particles;
5. 50 parts of carboxyl-containing acrylic monomer; 50 parts of nitrile group-containing acrylonitrile monomer; 7 parts of an initiator; 18 parts of a foaming agent; 5 parts of a nucleating agent; 15 parts of pre-foaming particles;
6. 45 parts of carboxyl-containing acrylic monomer; 60 parts of nitrile group-containing acrylonitrile monomer; 10 parts of an initiator; 25 parts of a foaming agent; 10 parts of a nucleating agent; 25 parts of pre-foaming particles;
7. 60 parts of carboxyl-containing acrylic monomer; 40 parts of nitrile group-containing acrylonitrile monomer; 10 parts of an initiator; 20 parts of foaming agent; 8 parts of a nucleating agent; 5 parts of pre-foaming particles.
In the above materials, the acrylic monomer containing a carboxyl group is selected from methacrylic acid and/or acrylic acid;
the nitrile group-containing acrylonitrile-based monomer is selected from methacrylonitrile and/or acrylonitrile.
In the above material, the initiator is at least one selected from tert-amyl peroxyacetate (TAPA), benzoyl Peroxide (BPO), tert-butyl peroxy-2-ethylhexanoate (TBPO), tert-amyl peroxybenzoate (TAPB), tert-butyl peroxybenzoate (TBPB), azobisisobutyronitrile (AIBN) and azobisisobutyronitrile (CABN);
the foaming agent is selected from at least one of ethanol, propanol, isopropanol, water, tert-butanol and amyl alcohol;
the nucleating agent is selected from at least one of carbamide, formamide, N-methylformamide and N, N-dimethylformamide.
In the above material, the preparation method of the pre-expanded particle comprises the following steps:
1) Mixing the carboxyl-containing acrylic monomer, nitrile-containing acrylonitrile monomer, initiator, foaming agent and nucleating agent according to a ratio to obtain a mixed solution;
2) Standing and polymerizing the mixed solution obtained in the step 1) under a sealed condition to obtain a polyacrylamide prepolymer;
3) Crushing the polyacrylamide prepolymer obtained in the step 2), dissolving the crushed polyacrylamide prepolymer in an organic solvent, controlling the system concentration to be below 20%, and filtering to obtain a prepolymer solution;
4) Precipitating the prepolymer solution obtained in the step 3) by using 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 pre-foaming particles.
The method adopts the steps 3) -4) to obtain the soluble prepolymer with large molecular weight and has certain purification effect.
In the step 2), the temperature of the standing polymerization can be 35-80 ℃, and the time can be 48-120 hours;
the static polymerization is carried out in a sealable cavity mold.
In the above material step 3), the organic solvent is at least one selected from N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, γ -butyrolactone, ethyl lactate, cyclopentanone, cyclohexanone, methyl ethyl ketone, ethyl acetate, and butyl acetate;
in the step 4), the low-boiling alcohol solvent is selected from at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol and 3-pentanol;
the drying temperature can be 60-100 ℃;
in the step 5), the heating temperature of the solid powder can be 170-220 ℃, and the time can be 10-60 min;
the pre-expanded particles can have a particle size of 1 to 30 μm and a density of 0.8 to 1.1g/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 polypropylene imide foam prepolymer copolymer;
(3) Heating and foaming the polypropylene imide foam prepolymer copolymer to obtain the high-strength high-toughness polypropylene imide foam material.
In the step (1), the mixing is performed under stirring, and the mixing time may be 1 to 8 hours, specifically 3, 4, 4.5, 5, or 3 to 5 hours;
in the step (2), the temperature of the polymerization reaction can be 40-150 ℃, the time can be 24-150 hours, the polymerization reaction is heated in a gradient heating mode, and the polymerization reaction is carried out after the temperature is raised to a certain temperature;
further, the gradient temperature rise mode is specifically as follows:
reacting for 30-60 hours at the temperature of 40-60 ℃, then increasing the temperature from 40-60 ℃ to 80-90 ℃ for 20-50 hours, and finally increasing the temperature from 80-90 ℃ to 100-140 ℃ for 30-60 hours;
in the step (3), the temperature for heating and foaming may be 180-250 ℃, specifically 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃ or 190-230 ℃, and the time may be 1-10 hours, specifically 4, 4.5, 5, 6, 7 hours or 4-7 hours.
In the step (2) of the preparation method, the polymerization reaction is carried out in the presence of an inert atmosphere, and the inert atmosphere comprises nitrogen and/or argon.
The invention further provides application of the high-strength and high-toughness polypropylene imide foam material in preparing any one of the following materials a) to d):
a) A high temperature resistant structural sandwich material having a requirement on the elongation at break of the foam material;
b) A high temperature resistant thermal insulation material;
c) A high temperature resistant sound insulating material;
d) High temperature resistant wave-transparent material.
The invention has the following advantages:
the pre-foaming particle toughened poly (meth) acrylimide foam material achieves the toughening effect through homogeneous polymerization of two same material systems, and can improve the elongation at break of the material without sacrificing the mechanical and thermal properties of the material; meanwhile, the pre-foaming particles have good compatibility with a material system, have small influence on the preparation process of the material, and do 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, the figure (a) is the product before modification, and the figure 1 (b) is the product after modification.
FIG. 2 PMI foam compressive strengths before and after toughening modification of inventive examples 1-2 versus comparative examples 1-2.
FIG. 3 is a comparison of PMI foam tensile strength before and after toughening modification of inventive examples 1-2 and comparative examples 1-2.
FIG. 4 is a comparison of PMI foam elongation at break before and after toughening modification of inventive examples 1-2 and comparative examples 1-2
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The preparation of the polypropylene imide based foam of the present invention is described below by way of specific examples, and it should be noted that "parts" used in the examples are expressed as "parts by weight" unless otherwise specified.
The invention adopts the pre-foaming 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 the pre-foaming 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-expanded polyacrylic imide particle in the following embodiment specifically comprises the following steps:
the method comprises the following steps: uniformly mixing a certain amount of carboxyl-containing acrylic monomers, nitrile-containing acrylonitrile monomers, an initiator, a foaming agent and a nucleating agent at room temperature (25 ℃) to obtain a uniform solution;
step two, injecting the solution obtained in the step one into a glass tube, sealing, standing and polymerizing for 48-120 hours at 35-80 ℃ to obtain a uniform polyacrylamide prepolymer;
step three: crushing the prepolymer obtained in the second step, dissolving the crushed prepolymer in an organic solvent such as dimethylacetamide, controlling the concentration to be below 20%, and filtering to obtain a uniform solution;
step four: precipitating the solution obtained in the third step by using solvents such as ethanol and the like, and drying at 60-100 ℃ to obtain solid powder;
step five: heating the solid obtained in the step four at 170-220 ℃ for 10-60 min, and crushing to obtain the pre-expanded particles of the polyacrylamide (called pre-expanded particles for short), wherein the particle size of the pre-expanded particles is 1-30 microns, and the density of the pre-expanded particles is 0.8-1.1 g/cm 3 Within the range, the standby is available.
Example 1
The preparation method of the polyacrylamide pre-foaming particle specifically comprises the following steps:
the method comprises the following steps: uniformly mixing 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 at room temperature (25 ℃) to obtain a uniform solution;
step two, injecting the solution obtained in the step one 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 step two, dissolving the crushed prepolymer in an organic solvent such as dimethylacetamide, controlling the concentration to be below 20%, and filtering to obtain a uniform solution;
step four: precipitating the solution obtained in the third step by using 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 200 ℃ for 45min, and crushing to obtain the pre-expanded particles of the polyacrylamide (referred to as pre-expanded particles for short), wherein the particle size of the pre-expanded particles is controlled to be 8-20 microns, and the density of the pre-expanded particles is controlled to be 0.9-1.0 g/cm 3 Within the range, for standby.
Preparing a high-strength high-toughness polypropylene imide foam material:
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-neck glass flask, and stirring for 4 hours at room temperature (25 ℃ C., 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: keeping the temperature at 60 ℃ for reacting for 50 hours, then heating from 60 ℃ to 90 ℃ for reacting for 30 hours, and finally heating from 90 ℃ to 130 ℃ for reacting for 50 hours to obtain a foam prepolymer copolymer resin plate;
3) Foaming the obtained foam prepolymer copolymer resin plate at 200 ℃ for 5 hours to obtain a polyacrylic imide foam plate blank;
machining the obtained polyacrylamide foam plate blank to obtain a polyacrylamide foam material with the density of 110kg/m 3 Uniform cell size, deformation at 180 deg.C/0.5 MPa/2h0.3%, compressive strength of 3.0MPa, tensile strength of 3.6MPa, modulus of 180MPa, and elongation at break of 5.1%.
The SEM result is shown in figure 1, and the comparison in the figure shows that the microstructure of the polyacrylamide foam material of the invention is not obviously changed, and the elongation at break is obviously improved.
Example 2
The preparation method of the pre-expanded particles in the embodiment 1 of the invention is different in that the raw materials adopted in the first step are as follows: 45 parts of methacrylic acid, 55 parts of methacrylonitrile, 8 parts of TBPO, 8 parts of formamide and 20 parts of isopropanol.
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-neck glass flask in sequence, 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: keeping the temperature at 60 ℃ for reacting for 50 hours, then heating from 60 ℃ to 90 ℃ for reacting for 30 hours, and finally heating from 90 ℃ to 120 ℃ for reacting for 50 hours to obtain a foam prepolymer copolymer resin plate;
foaming the obtained foam prepolymer copolymer resin plate for 4.5 hours at 210 ℃ to obtain a polyacrylic imide foam plate blank;
machining the obtained polyacrylamide foam plate blank to obtain a polyacrylamide foam material with the density of 108kg/m 3 The cells are uniform, the deformation 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-neck 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: reacting for 50 hours at the temperature of 60 ℃, heating from 60 ℃ to 90 ℃ for 30 hours, and finally heating from 90 ℃ to 130 ℃ for 50 hours to obtain a foam prepolymer copolymer resin plate;
foaming the obtained foam prepolymer copolymer resin plate at 200 ℃ for 5 hours to obtain a polyacrylic imide foam plate blank;
machining the obtained polyacrylamide foam plate blank to obtain a polyacrylamide foam material with the density of 110kg/m 3 The cells are uniform, the deformation 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
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-neck glass flask in sequence, 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: keeping the temperature at 60 ℃ for reacting for 50 hours, then heating from 60 ℃ to 90 ℃ for reacting for 30 hours, and finally heating from 90 ℃ to 120 ℃ for reacting for 50 hours to obtain a foam prepolymer copolymer resin plate;
foaming the obtained foam prepolymer copolymer resin plate for 4.5 hours at 210 ℃ to obtain a polyacrylic imide foam plate blank;
machining the obtained polyacrylamide foam plate blank to obtain a polyacrylamide foam material with the density of 108kg/m 3 The cells are uniform, the deformation 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 conjunction with the results of FIGS. 2 to 4, the density of the foam sheet material of the polyacrylimide of example 1 of the present invention was 110kg/m 3 Elongation at break of 5.1%, while in comparative example 1 at the same density, elongation at break was only 2.8%; book (I)The density of the polyacrylamide foam board blank in inventive example 2 was 108kg/m 3 Elongation at break was 5.2%, while the same density as in comparative example 2, the elongation at break was only 2.8%. Therefore, the comparison of the data of the example 1 and the comparative example 1 and the comparison of the data of the example 2 and the comparative example 2 respectively show that the toughness of the obtained polyacrylic imide foam material is better by adopting the pre-foaming particles of the same material system as the PMI foam continuous phase.
Example 3
The preparation method of the pre-expanded particles in the embodiment 1 of the invention is different in that the raw materials adopted in the first step are 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 carbamide, 20 parts of tert-butyl alcohol and 5 parts of water.
Sequentially adding 50 parts of methacrylic acid, 50 parts of acrylonitrile, 10 parts of pre-foaming particles, 7 parts of CABP, 8 parts of TAPB, 5 parts of formamide, 2 parts of carbamide, 20 parts of tert-butyl alcohol and 5 parts of water into a three-neck 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: reacting at 60 ℃ for 55 hours in a heat preservation way, then heating from 60 ℃ to 80 ℃ for 20 hours, and finally heating from 80 ℃ to 100 ℃ for 40 hours to obtain a 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;
machining the obtained polyacrylic imide foam plate blank to obtain a polyacrylic imide foam material with the density of 75kg/m 3 The cells are uniform, the deformation 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 preparation method of the pre-expanded particles in the embodiment 1 of the invention is different in that the raw materials adopted in the first step are as follows: 45 parts of methacrylic acid, 55 parts of acrylonitrile, 10 parts of TAPB, 5 parts of formamide, 2 parts of carbamide, 15 parts of tert-butanol and 3 parts of water.
Adding 45 parts of methacrylic acid, 55 parts of acrylonitrile, 35 parts of prefoamed particles, 10 parts of TAPB, 5 parts of formamide, 2 parts of carbamide, 15 parts of tert-butyl alcohol and 3 parts of water into a three-neck glass flask in sequence, and stirring 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: reacting for 60 hours at 50 ℃, heating from 50 ℃ to 90 ℃ for 20 hours, and finally heating from 90 ℃ to 120 ℃ for 60 hours to obtain a foam prepolymer copolymer resin plate;
foaming the obtained foam prepolymer copolymer resin plate for 4 hours at 230 ℃ to obtain a polyacrylic imide foam plate blank;
machining the obtained polyacrylamide foam plate blank to obtain a polyacrylamide foam material with the density of 80kg/m 3 The cells are uniform, the deformation 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 preparation method of the pre-expanded particles in the embodiment 1 of the invention is different in that the raw materials adopted in the first step are 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-butyl alcohol and 3 parts of water.
Sequentially adding 50 parts of methacrylic acid, 50 parts of methacrylonitrile, 15 parts of prefoamed particles, 5 parts of TAPB, 2 parts of BPO, 3 parts of formamide, 2 parts of N-methylformamide, 15 parts of tert-butyl alcohol and 3 parts of water into a three-neck glass flask, and stirring at room temperature for 5 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: keeping the temperature at 60 ℃ for reacting for 60 hours, then heating from 60 ℃ to 90 ℃ for reacting for 20 hours, and finally heating from 90 ℃ to 140 ℃ for reacting for 60 hours to obtain a foam prepolymer copolymer resin plate;
foaming the obtained foam prepolymer copolymer resin plate at 190 ℃ for 7 hours to obtain a polyacrylamide foam plate blank;
machining the obtained polyacrylamide foam plate blank to obtain a polyacrylamide foam material with the density of 200kg/m 3 The cells are uniform, the deformation 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 preparation method of the pre-expanded particles in the embodiment 1 of the invention is different in that the raw materials adopted in the first step are 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.
Adding 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 into a three-neck glass flask in sequence, and stirring 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: reacting for 30 hours at the temperature of 40 ℃, heating from 40 ℃ to 90 ℃ for 50 hours, and finally heating from 90 ℃ to 110 ℃ for 50 hours to obtain a foam prepolymer copolymer resin plate;
foaming the obtained foam prepolymer copolymer resin plate at 200 ℃ for 5 hours to obtain a polyacrylic imide foam plate blank;
machining the obtained polyacrylamide foam plate blank to obtain a polyacrylamide foam material with the density of 150kg/m 3 The cells are uniform, the deformation 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 preparation method of the pre-expanded particles in the embodiment 1 of the invention is different in that the raw materials adopted in the first step are 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.
Adding 60 parts of methacrylic acid, 40 parts of methacrylonitrile, 5 parts of pre-expanded particles, 5 parts of AIBN, 5 parts of TAPB, 8 parts of formamide and 20 parts of isopropanol into a three-neck glass flask in sequence, and stirring 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: reacting at 50 ℃ for 40 hours in a heat preservation way, then reacting at 50 ℃ for 20 hours from the temperature rise to 70 ℃, then reacting at 70 ℃ to 80 ℃ for 20 hours, and finally reacting at 80 ℃ to 110 ℃ for 30 hours to obtain a foam prepolymer copolymer resin plate;
foaming the obtained foam prepolymer copolymer resin plate at 210 ℃ for 4.5 hours to obtain a polyacrylamide foam plate blank;
machining the obtained polyacrylic imide foam plate blank to obtain the polyacrylic imide foam material with the density of 115kg/m 3 The cells are uniform, the deformation 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 in the above 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 machined into a foam board with the required size, fiber (or cloth)/AG 80 epoxy prepreg (0 degree/90 degrees/0 degree/90 degrees) is respectively paved on the surface of the PMI foam, a press is adopted for limiting and curing molding, and the curing process is 180 degrees/0.3 MPa/2h, so that the PMI sandwich composite material is prepared. The material is suitable for the field of light high-strength composite materials. PMI foams of different densities can be prepared into PMI sandwich composites of different strengths. Generally, the higher the PMI density, the higher the strength of the PMI sandwich composite.
In conclusion, the PMI foam not only has excellent heat resistance and mechanical properties, but also has low dielectric constant and thermal conductivity, so that the PMI foam has a wide application prospect in the field of structural function integration of high-temperature resistance, wave transmission, heat insulation and the like.
The embodiment of the invention provides a preparation method of a high-strength high-toughness polypropylene imide foam material, the prepared polypropylene imide foam material adopts the pre-foaming particles, the prepared PMI foam has the characteristics of high closed cell rate, good high-temperature resistance, high compressive strength and the like, and the density of the prepared foam is 50-250 kg/m 3 The closed porosity is more than 90 percent, and the thermal deformation temperature is not less than 200 ℃. E.g. a density of 110kg/m at room temperature 3 The compressive strength of the foam is not less than 2.5MPa; the density of the polyacrylamide foam board prepared in the embodiment 1 of the invention is 110kg/m at high temperature of 180 ℃ and pressure of 0.5MPa 3 The foam of (2) has a compression set of less than 1% after a 2 hour process.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are 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:
the pre-foaming particle comprises the following components in parts by mass: 50 parts of carboxyl-containing acrylic monomer; 1-100 parts of nitrile group-containing acrylonitrile monomer; 0.1-50 parts of an initiator; 0.1-50 parts of foaming agent; 0.1 to 50 portions of nucleating agent.
2. The material of claim 1, wherein: the acrylic monomer containing carboxyl is selected from methacrylic acid and/or acrylic acid;
the nitrile group-containing acrylonitrile-based monomer is selected from methacrylonitrile and/or acrylonitrile.
3. The material of claim 1, wherein: the initiator is at least one selected from tert-amyl peroxyacetate, benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxybenzoate, tert-butyl peroxybenzoate, azobisisobutyronitrile and azobisisobutyronitrile formamide;
the foaming agent is selected from at least one of ethanol, propanol, isopropanol, water, tert-butanol and amyl alcohol;
the nucleating agent is selected from at least one of carbamide, formamide, N-methylformamide and N, N-dimethylformamide.
4. A material according to any one of claims 1 to 3, wherein: the preparation method of the pre-expanded particles comprises the following steps:
1) Mixing the carboxyl-containing acrylic monomer, nitrile-containing acrylonitrile monomer, initiator, foaming agent and nucleating agent according to a ratio to obtain a mixed solution;
2) Standing and polymerizing the mixed solution obtained in the step 1) under a sealed condition to obtain a polyacrylamide prepolymer;
3) Crushing the polyacrylamide prepolymer obtained in the step 2), dissolving the crushed polyacrylamide prepolymer in an organic solvent, controlling the system concentration to be below 20%, and filtering to obtain a prepolymer solution;
4) Precipitating the prepolymer solution obtained in the step 3) by using 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 pre-foaming particles.
5. The material of claim 4, wherein: in the step 2), the temperature of the standing polymerization is 35-80 ℃, and the time is 48-120 hours;
the static polymerization is carried out in a sealable cavity mold.
6. A material according to claim 4 or 5, characterized in that: 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 low-boiling alcohol solvent is selected from at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol and 3-pentanol;
the drying temperature is 60-100 ℃;
in the step 5), the solid powder is heated at the temperature of 170-220 ℃ for 10-60 min;
the particle diameter of the pre-foaming particles is 1-30 mu m, and the density is 0.8-1.1 g/cm 3 。
7. A method of preparing the material of any one of claims 1-6, 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 polypropylene imide foam prepolymer copolymer;
(3) Heating and foaming the polypropylene imide foam prepolymer copolymer to obtain the high-strength high-toughness polypropylene imide foam material.
8. The method for producing according to claim 7, characterized in that: in the step (1), the mixing is carried out under the condition of stirring, 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; heating the polymerization reaction in a gradient temperature rise mode, and then carrying out heat preservation reaction;
in the step (3), the heating foaming temperature is 180-250 ℃ and the time is 1-10 hours.
9. The production method according to claim 7 or 8, characterized in that: in step (2), the polymerization reaction is carried out in the presence of an inert atmosphere, which comprises nitrogen and/or argon.
10. Use of a high strength and high toughness polypropyleneimide foam according to any one of claims 1 to 6 for the preparation of any one of the following a) to d):
a) High-temperature-resistant structural sandwich material with requirement on elongation at break of foam material
b) A high temperature resistant thermal insulation material;
c) A high temperature resistant sound insulating material;
d) High temperature resistant wave-transparent material.
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Citations (3)
| 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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Patent Citations (3)
| 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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