CN112341815A - Radiation-resistant polyimide foam material, and preparation method and application thereof - Google Patents

Radiation-resistant polyimide foam material, and preparation method and application thereof Download PDF

Info

Publication number
CN112341815A
CN112341815A CN202011383778.7A CN202011383778A CN112341815A CN 112341815 A CN112341815 A CN 112341815A CN 202011383778 A CN202011383778 A CN 202011383778A CN 112341815 A CN112341815 A CN 112341815A
Authority
CN
China
Prior art keywords
foam material
polyimide foam
radiation
resistant polyimide
cerium oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202011383778.7A
Other languages
Chinese (zh)
Other versions
CN112341815B (en
Inventor
周光远
聂赫然
周鹤
黄志成
顾铭茜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changzhou Fulong New Technology Materials Co ltd
Original Assignee
Jiangsu Zhongke Polymer New Material Industry Technology Research Institute Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Zhongke Polymer New Material Industry Technology Research Institute Co Ltd filed Critical Jiangsu Zhongke Polymer New Material Industry Technology Research Institute Co Ltd
Priority to CN202011383778.7A priority Critical patent/CN112341815B/en
Publication of CN112341815A publication Critical patent/CN112341815A/en
Application granted granted Critical
Publication of CN112341815B publication Critical patent/CN112341815B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—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
    • C08J9/125—Water, e.g. hydrated salts
    • 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
    • C08J2203/10—Water or water-releasing compounds
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences

Landscapes

  • 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)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides an irradiation-resistant polyimide foam material, which contains cerium oxide particles; the irradiation-resistant polyimide foam material has a porous structure; the cerium oxide particles are compounded in the polyimide foam. The polyimide foam material provided by the invention contains the cerium oxide particles which have a barrier and shielding effect on nuclear radiation and are environment-friendly, a specific composite form combining physical composite and chemical bonding is realized, the cerium oxide can be effectively ensured to be uniformly dispersed in a polyimide foam system, the irradiation resistance of the polyimide foam material is further effectively improved, and no threat is caused to the environment. The radiation-resistant polyimide foam material provided by the invention has the advantages of simple preparation process, easiness in control, contribution to realizing industrial continuous production and important reference significance for improving the safety performance of nuclear powered ships and meeting the environmental protection requirement.

Description

Radiation-resistant polyimide foam material, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polyimide foam materials, relates to an irradiation-resistant polyimide foam material, and a preparation method and application thereof, and particularly relates to a marine irradiation-resistant polyimide foam material, and a preparation method and application thereof.
Background
The polyimide foam material is a light porous material, and has the properties of light weight, excellent high and low temperature resistance, heat insulation, sound absorption, noise reduction, flame retardance, insulation and the like. The high-performance polyimide foam can resist 250-300 ℃ for a long time and 400-500 ℃ for a short time, and is one of the materials with the best heat stability in organic polymers. The high-performance radiation-resistant polyimide foam material can resist extremely low temperature, does not have the advantages of brittle fracture in liquid helium at the temperature of 269 ℃ below zero and the like, has been successfully developed in the 60 th century since 20 th, and has attracted extensive attention in the field of high polymer materials by virtue of excellent performances of high and low temperature resistance, flame retardance, fire resistance, sound absorption, noise reduction, oxidation resistance, hydrolysis resistance and the like, so that the rapid development of the polyimide foam material industry is promoted. In recent years, the polyimide foam material has wide application in the fields of military national defense, aerospace, ship and warship, rail traffic, electronics, new energy and the like, and more than 15 countries have been reported to apply the polyimide foam material as a heat insulation material to a naval vessel system of the naval vessel, wherein the national defense department designates the polyimide foam material as a special heat insulation material for naval vessels. In addition, the polyimide foam material is widely applied to civil ship systems, such as luxury cruise ships, yachts and liquefied natural gas ships.
With the continuous depletion of petroleum resources and the continuous improvement of environmental protection requirements, from the technical and economic perspectives, a nuclear powered ship which does not depend on fossil fuels, has zero pollution emission and ultra-long endurance capacity becomes the development direction of the future ship. Nuclear powered marine nuclear power plants have a large amount of high energy radiation due to fission in the reactor. Polyimide foam is used as an important heat and sound insulation material for ships, accounts for more than 40% of the ship interior materials, and is widely applied to various places such as shells, bulkheads, cabin roofs, cooling water pipelines, high-temperature steam pipelines and the like of ships. If the polyimide foam heat and sound insulation material which is not modified is subjected to nuclear radiation for a long time, the mechanical performance, the heat insulation performance, the sound absorption performance and the like of the polyimide foam heat and sound insulation material are greatly reduced, so that the effective isolation and protection of equipment and personnel in a ship can not be realized; more severe conditions may lead to failure of the material, causing thermal runaway that threatens the safety of ships and personnel. Therefore, the polyimide foam is used as a heat-insulating and sound-insulating material special for ships, and the improvement of the irradiation resistance of the polyimide foam is very important.
Related researches are also disclosed in the prior art, for example, in patent US6608319B2, tungsten carbide and boron carbide are selected as gamma ray shielding materials, and vulcanized silicone rubber with good irradiation resistance is prepared under the synergistic effect of barium sulfate, diamond, target wool and the like, but the strength is low and the process is complicated. In contrast, patent CN1970636A selects phenyl silicone rubber to prepare rubber with radiation resistance, but its rebound resilience and mechanical strength are obviously reduced. The reported radiation-resistant materials contain lead, phenyl and other substances which have potential pollution to the environment, and the production cost is high and the radiation resistance is limited. Therefore, the requirements of the material on the irradiation resistance and the environmental protection in the application field cannot be met by selecting the traditional heavy metal additives such as lead, tungsten, barium and the like and introducing phenyl groups into the main chain or the side chain.
Therefore, how to improve the irradiation resistance of the polyimide foam, so that the polyimide foam can be used as a heat and sound insulation material for a nuclear power ship, which has a very important significance in solving the problems existing in the practical application, improving the safety of the ship and meeting the environmental protection requirements, is also one of the focuses of various research and development manufacturers and a line of researchers.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an irradiation-resistant polyimide foam material, a preparation method and an application thereof, and in particular, an irradiation-resistant polyimide foam material for ships, wherein cerium oxide which has a barrier shielding effect on nuclear radiation and is environmentally friendly is compounded in the irradiation-resistant polyimide foam material provided by the present invention, such that irradiation resistance of the polyimide foam material for ships can be effectively improved, and important reference significance is provided for enhancing safety performance of nuclear powered ships and meeting environmental protection requirements; and the process is simple and easy to control, and is favorable for realizing industrial continuous production.
The invention provides an irradiation-resistant polyimide foam material, which contains cerium oxide particles;
the irradiation-resistant polyimide foam material has a porous structure;
the cerium oxide particles are compounded in the polyimide foam.
Preferably, the particle size of the cerium oxide particles is 0.5-4 μm;
the mass content of the cerium oxide particles is 5-15%;
the pore diameter of the porous structure is 100-700 mu m;
the combination mode of the cerium oxide and the polyimide comprises chemical bond bonding;
the radiation-resistant polyimide foam material comprises a radiation-resistant polyimide foam material for ships.
Preferably, the opening rate of the radiation-resistant polyimide foam material is 80-99%;
the density of the radiation-resistant polyimide foam material is 9-12 kg/m3；
The cerium oxide particles are filled in the cell gaps, positioned in the cells and attached to the cell walls of the cells;
cerium ions in the cerium oxide are bonded with N and/or O atoms in an imide ring in a polyimide structure through coordination bonds;
the radiation-resistant polyimide foam material also comprises a foam stabilizer.
The invention provides an irradiation-resistant polyimide foam material, which comprises the following raw materials in percentage by mass:
Figure BDA0002809164630000031
preferably, the isocyanate comprises one or more of PM-200, NE-466, PM-400, PM-700, 8122, 8214 and PM-8223;
the aromatic dianhydride comprises one or more of BTDA, PMDA and DSDA;
the solvent comprises one or more of DMSO, DMF, and DMAC;
the catalyst comprises a metal catalyst and/or an amine catalyst.
Preferably, the isocyanate content is 28-35%;
the blowing agent comprises one or more of acetone, water, methanol, ethanol and 2-butoxyethanol;
the foam stabilizer comprises one or more of polyether modified silicone oil, silicone oil and water-soluble silicone oil;
the catalyst comprises one or more of dibutyltin dilaurate, stannous octoate, bismuth isooctanoate, N, N-dimethyl cyclohexylamine, N, N, N ', N ' -tetramethyl alkylene diamine and N, N ' -diethyl piperazine.
The invention provides an irradiation-resistant polyimide foam material as described in any one of the above technical schemes or a preparation method of the irradiation-resistant polyimide foam material as described in any one of the above technical schemes, which comprises the following steps:
1) mixing aromatic dianhydride and a solvent to obtain a first solution;
mixing the cerium oxide, water, a foaming agent, a foam stabilizer and a catalyst again to obtain a second solution;
2) premixing the first solution and the second solution obtained in the step, finally mixing the premixed solution and isocyanate, then carrying out foaming molding in a mold, and finally curing to obtain the radiation-resistant polyimide foam material.
Preferably, the mixing mode comprises heating and stirring;
the mixing temperature is 60-80 ℃;
the mixing speed is 300-500 r/min;
the mixing time is 6-12 h;
the means of remixing comprises ultrasonic mixing;
the power of ultrasonic mixing is 100-150W;
the remixing time is 10-15 min.
Preferably, the final mixing mode comprises high-speed stirring and mixing;
the rotating speed of the final mixing is 1000-3000 r/min;
the final mixing time is 15-30 s;
the foaming and forming time is 15-20 min;
the curing temperature is 200-300 ℃;
the curing time is 4-8 h.
The invention also provides the application of the radiation-resistant polyimide foam material in any one of the technical schemes, the radiation-resistant polyimide foam material in any one of the technical schemes or the radiation-resistant polyimide foam material prepared by the preparation method in any one of the technical schemes in the field of ships.
The invention provides an irradiation-resistant polyimide foam material, which contains cerium oxide particles; the irradiation-resistant polyimide foam material has a porous structure; the cerium oxide particles are compounded in the polyimide foam. Compared with the prior art, the invention aims at the problems that the existing radiation-resistant material has low strength and complex process, or the rebound resilience and the mechanical strength are obviously reduced, and the like. Moreover, the reported radiation-resistant materials all contain lead, phenyl and other substances which have potential pollution to the environment, the production cost is high, the radiation-resistant performance is limited, and the defects that the traditional heavy metal additives such as lead, tungsten, barium and the like are selected, and the radiation-resistant performance requirement of the materials and the environmental protection requirement in the application field cannot be met by introducing the phenyl into the main chain or the side chain and the like are overcome.
The invention particularly designs an irradiation-resistant polyimide foam material, which contains cerium oxide particles, and the cerium oxide particles are compounded in porous polyimide foam in a specific form. The polyimide foam material provided by the invention contains environment-friendly nano cerium oxide particles with a barrier and shielding effect on nuclear radiation, and the outer layer hollow orbit of rare earth ions and lone pair electrons or unshared pair electrons provided by N and/or O atoms in an imide ring are effectively combined to form a bonding effect, so that a specific combination form of combining physical combination and chemical combination is realized, and the radiation resistance of the polyimide foam material is effectively improved. Compared with the traditional shielding material of heavy metals such as lead, tungsten, barium and the like with chemical toxicity, the cerium oxide can effectively improve the irradiation resistance of the polyimide foam material and has no threat to the environment. The cerium oxide can effectively improve the radiation resistance of the material, and mainly has the advantages that when radiation passes through the cerium oxide, a photoelectric effect, a Compton effect and an electron pair effect which can absorb or scatter radiation such as X rays and gamma rays can occur, so that the cerium oxide has the effect of blocking and shielding the radiation. The stable bonding effect formed by the effective combination of the outer layer hollow orbit of the rare earth ions and lone pair electrons or unshared pair electrons provided by N and O atoms in the imide ring can effectively ensure that cerium oxide is uniformly dispersed in a polyimide foam system.
The radiation-resistant polyimide foam material provided by the invention has the advantages of simple preparation process, easiness in control and contribution to realizing industrial continuous production, can effectively improve the radiation resistance of the marine polyimide foam material, and has important reference significance for improving the safety performance of nuclear power ships and meeting the environmental protection requirement.
Experimental results show that the radiation-resistant polyimide foam provided by the invention has small influence on mechanical properties after being irradiated, and has small attenuation on tensile strength, tear strength and compressive strength, but is obviously superior to the polyimide foam which is not added with cerium oxide particles after being irradiated. The addition of cerium oxide particles improves the radiation resistance of the polyimide foam.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All of the starting materials of the present invention are not particularly limited in their purity, and the present invention preferably employs purity requirements that are conventional in the analytical or marine polyimide foam manufacturing arts.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
The invention provides an irradiation-resistant polyimide foam material, which contains cerium oxide particles;
the irradiation-resistant polyimide foam material has a porous structure;
the cerium oxide particles are compounded in the polyimide foam.
The particle size of the cerium oxide particles is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, the radiation resistance of the polyimide foam material is better improved, the structure of a material main body is ensured, the original performance of the foam material is ensured, and the performance reduction after irradiation is reduced, wherein the particle size of the cerium oxide particles is preferably 0.5-4 μm, more preferably 0.6-3 μm, more preferably 0.7-2 μm, and more preferably 0.8-1 μm. The cerium oxide particles of the present invention are preferably cerium oxide particles obtained by ultrasonic shearing, i.e., nano-sized cerium oxide particles.
The invention is not particularly limited in principle to the mass content of the cerium oxide particles, and a person skilled in the art can select and adjust the cerium oxide particles according to actual production conditions, application requirements and quality control, in order to better improve the radiation resistance of the polyimide foam material, ensure the structure of the material main body, ensure the original performance of the foam material and reduce the performance reduction after radiation, the mass content of the cerium oxide particles is preferably 5-15%, more preferably 7-13%, and more preferably 9-11%.
The specific mode of combining the cerium oxide and the polyimide is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control. Specifically, the cerium ion in the cerium oxide is preferably bonded to the N and/or O atom in the imide ring in the polyimide structure through a coordinate bond. In the invention, cerium can be respectively coordinated with N or O in an imide ring independently or simultaneously coordinated with the N or O to form monodentate coordination and/or multidentate coordination.
The specific pore size of the irradiation-resistant polyimide foam material with the porous structure is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, the irradiation-resistant polyimide foam material with the porous structure preferably has a pore size of 100-700 microns, more preferably 200-600 microns, and more preferably 300-500 microns, so that the irradiation-resistant performance of the polyimide foam material is better improved, the structure of a material main body is ensured, the original performance of the foam material is ensured, and the performance reduction after irradiation is reduced.
The invention has no special limitation on the aperture ratio of the radiation-resistant polyimide foam material in principle, and a person skilled in the art can select and adjust the aperture ratio according to the actual production condition, application requirements and quality control, in order to better improve the radiation-resistant performance of the polyimide foam material, ensure the structure of a material main body, ensure the original performance of the foam material and reduce the performance reduction after radiation, the aperture ratio of the radiation-resistant polyimide foam material is preferably 80-99%, more preferably 84-95%, and more preferably 88-91%.
The density of the irradiation-resistant polyimide foam material is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, the irradiation-resistant polyimide foam material disclosed by the invention is used for better improving the irradiation-resistant performance of the polyimide foam material, ensuring the structure of a material main body, ensuring the original performance of the foam material and reducing the performance reduction after irradiation, and the density of the irradiation-resistant polyimide foam material is preferably 9-12 kg/m3More preferably 9.5 to 11.5kg/m3More preferably 10 to 11kg/m3。
The compounding position of the cerium oxide particles is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, and the cerium oxide particles are preferably filled in one or more of the cell gaps, the cell holes and the cell wall of the cell, more preferably filled in the cell gaps, the cell holes and the cell wall of the cell, in order to better improve the irradiation resistance of the polyimide foam, ensure the structure of the material main body, ensure the original performance of the foam and reduce the performance reduction after irradiation.
The radiation-resistant polyimide foam material is not particularly limited in specific application in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control.
The invention is a complete and refined integral preparation process, better improves the radiation resistance of the polyimide foam material, ensures the structure of the material main body, ensures the original performance of the foam material, and reduces the performance reduction after radiation, and the radiation-resistant polyimide foam material also preferably comprises a foam stabilizer.
The invention provides an irradiation-resistant polyimide foam material, which comprises the following raw materials in percentage by mass:
Figure BDA0002809164630000071
Figure BDA0002809164630000081
in the radiation-resistant polyimide foam material of the present invention, the structural selection, composition, and parameters, and the corresponding preferred principles, preferably remain the same as the structural selection, composition, and parameters, and the corresponding preferred principles in the radiation-resistant polyimide foam material, and are not described in detail herein. In the present invention, the parts by weight and the mass percentages are only different in terms of expressions and the same in essential meanings, and those skilled in the art can understand the correct meanings based on the general knowledge and can uniquely determine the same.
The addition amount of the isocyanate is 15 to 63 parts by weight, preferably 20 to 58 parts by weight, more preferably 25 to 53 parts by weight, more preferably 30 to 48 parts by weight, and more preferably 35 to 43 parts by weight. The specific selection of the isocyanate is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, so that the radiation resistance of the polyimide foam material is better improved, the structure of a material main body is ensured, the original performance of the foam material is ensured, and the performance reduction after radiation is reduced, wherein the isocyanate preferably comprises one or more of PM-200, NE-466, PM-400, PM-700, 8122, 8214 and PM-8223, more preferably PM-200, NE-466, PM-400, PM-700, 8122, 8214 or PM-8223, and specifically can be PM-200 produced by Wanhua chemistry, NE-466 produced by Wanhua chemistry, PM-400 produced by Wanhua chemistry, PM-700 produced by Wanhua chemistry, PM-466 produced by Wanhua chemistry, PM-400 produced by Wanhua chemistry, PM-700 produced by Wanhua, 8122 produced by Van Waals chemical, 8214 produced by Van Waals chemical or PM-8223 produced by Van Waals chemical. The isocyanate content of the isocyanate is preferably 28-35%, more preferably 29-34%, more preferably 30-33%, and more preferably 31-32%.
The aromatic dianhydride is added in an amount of 19 to 66 parts by weight, preferably 29 to 56 parts by weight, and more preferably 39 to 46 parts by weight. The specific choice of the aromatic dianhydride is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, and the aromatic dianhydride preferably comprises one or more of BTDA, PMDA and DSDA, more preferably BTDA, PMDA or DSDA, in order to better improve the radiation resistance of the polyimide foam material, ensure the structure of the material body, ensure the original performance of the foam material and reduce the performance reduction after radiation.
The addition amount of the solvent is 15-41 parts by weight, preferably 20-36 parts by weight, and more preferably 25-31 parts by weight. The specific choice of the solvent is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control.
The addition amount of the foaming agent is 0-25 parts by weight, preferably 5-20 parts by weight, and more preferably 10-15 parts by weight. The specific selection of the foaming agent is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to actual production conditions, application requirements and quality control, and the invention is to better improve the radiation resistance of the polyimide foam material, ensure the structure of the material main body, ensure the original performance of the foam material and reduce the performance reduction after radiation, wherein the foaming agent preferably comprises one or more of acetone, water, methanol, ethanol and 2-butoxyethanol, and more preferably acetone, water, methanol, ethanol or 2-butoxyethanol.
The addition amount of the foam stabilizer is 2-14 parts by weight, preferably 5-11 parts by weight, and more preferably 8-9 parts by weight. The concrete selection of the foam homogenizing agent is not particularly limited in principle, and a person skilled in the art can select and adjust the foam homogenizing agent according to actual production conditions, application requirements and quality control.
The addition amount of the catalyst is 0.1-8.5 parts by weight, preferably 2-6.5 parts by weight, and more preferably 4-4.5 parts by weight. The concrete selection of the foam stabilizer is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to the actual production condition, application requirements and quality control. More specifically, the catalyst preferably includes one or more of dibutyltin dilaurate, stannous octoate, bismuth isooctanoate, N-dimethylcyclohexylamine, N '-tetramethylalkylenediamine, and N, N' -diethylpiperazine, and more preferably dibutyltin dilaurate, stannous octoate, bismuth isooctanoate, N-dimethylcyclohexylamine, N '-tetramethylalkylenediamine, or N, N' -diethylpiperazine.
The adding amount of the water is 20-40 parts by weight, preferably 24-36 parts by weight, and more preferably 28-32 parts by weight.
The cerium oxide is added in an amount of 5 to 15 parts by weight, preferably 8 to 13 parts by weight, and more preferably 10 to 11 parts by weight.
The invention provides an irradiation-resistant polyimide foam material as defined in any one of the above technical schemes or a preparation method of the irradiation-resistant polyimide foam material as defined in any one of the above technical schemes, which comprises the following steps:
1) mixing aromatic dianhydride and a solvent to obtain a first solution;
mixing the cerium oxide, water, a foaming agent, a foam stabilizer and a catalyst again to obtain a second solution;
2) premixing the first solution and the second solution obtained in the step, finally mixing the premixed solution and isocyanate, then carrying out foaming molding in a mold, and finally curing to obtain the radiation-resistant polyimide foam material.
In the radiation-resistant polyimide foam material of the present invention, the selection and proportion of the raw materials and the preferred range thereof are preferably consistent with those of the radiation-resistant polyimide foam material, and are not described herein again.
The method comprises the steps of firstly mixing aromatic dianhydride and a solvent to obtain a first solution.
And mixing the cerium oxide, the water, the foaming agent, the foam stabilizer and the catalyst again to obtain a second solution.
The mixing mode is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control.
The temperature of the mixing is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, the radiation resistance of the polyimide foam material is better improved, the structure of a material main body is ensured, the original performance of the foam material is ensured, the performance reduction after radiation is reduced, and the mixing temperature is preferably 60-80 ℃, more preferably 64-76 ℃, and more preferably 68-72 ℃.
The rotation speed of the mixing is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, the radiation resistance of the polyimide foam material is better improved, the structure of a material main body is ensured, the original performance of the foam material is ensured, and the performance reduction after radiation is reduced, wherein the rotation speed of the mixing is preferably 300-500 r/min, more preferably 340-460 r/min, and more preferably 380-420 r/min.
The mixing time is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, the irradiation resistance of the polyimide foam material is better improved, the structure of a material main body is guaranteed, the original performance of the foam material is guaranteed, the performance reduction after irradiation is reduced, and the mixing time is preferably 6-12 hours, more preferably 7-11 hours, and more preferably 8-10 hours.
The remixing mode is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control.
The power of ultrasonic mixing is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, the power of ultrasonic mixing is preferably 100-150W, more preferably 110-140W, and more preferably 120-130W, so that the irradiation resistance of the polyimide foam material is better improved, the structure of a material main body is ensured, the original performance of the foam material is ensured, and the performance reduction after irradiation is reduced.
The remixing time is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, the remixing time is preferably 10-15 min, more preferably 11-14 min, and more preferably 12-13 min, so that the irradiation resistance of the polyimide foam material is better improved, the structure of the material main body is ensured, the original performance of the foam material is ensured, and the performance reduction after irradiation is reduced.
The invention finally pre-mixes the first solution and the second solution obtained in the above steps, then mixes the pre-mixed solution with isocyanate, then carries out foaming molding in a mould, and finally cures to obtain the radiation-resistant polyimide foam material.
The final mixing mode is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control.
The rotation speed of the final mixing is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, the radiation resistance of the polyimide foam material is better improved, the structure of a material main body is ensured, the original performance of the foam material is ensured, and the performance reduction after radiation is reduced, wherein the rotation speed of the final mixing is preferably 1000-3000 r/min, more preferably 1400-2600 r/min, and more preferably 1800-2200 r/min.
The final mixing time is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, the irradiation resistance of the polyimide foam material is better improved, the structure of a material main body is guaranteed, the original performance of the foam material is guaranteed, the performance reduction after irradiation is reduced, and the final mixing time is preferably 15-30 s, more preferably 18-27 s, and more preferably 21-24 s.
The foaming forming time is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, the irradiation resistance of the polyimide foam material is better improved, the structure of a material main body is guaranteed, the original performance of the foam material is guaranteed, the performance reduction after irradiation is reduced, and the foaming forming time is preferably 15-20 min, more preferably 16-19 min, and more preferably 17-18 min.
The curing temperature is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, the radiation resistance of the polyimide foam material is better improved, the structure of a material main body is ensured, the original performance of the foam material is ensured, the performance reduction after radiation is reduced, and the curing temperature is preferably 200-300 ℃, more preferably 220-280 ℃, and more preferably 240-260 ℃.
The curing time is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual production conditions, application requirements and quality control, the radiation resistance of the polyimide foam material is better improved, the structure of a material main body is guaranteed, the original performance of the foam material is guaranteed, the performance reduction after radiation is reduced, and the curing time is preferably 4-8 hours, more preferably 4.5-7.5 hours, more preferably 5-7 hours, and more preferably 5.5-6.5 hours.
The invention is a complete and refined whole preparation process, better improves the radiation resistance of the polyimide foam material, ensures the structure of the material main body, ensures the original performance of the foam material, and reduces the performance reduction after radiation, and the preparation process of the radiation-resistant polyimide foam material can specifically comprise the following steps:
(1) mixing 19-66 parts of aromatic dianhydride and 15-41 parts of solvent, heating and stirring;
(2) mixing 5-15 parts of cerium oxide and 20-40 parts of water, ultrasonically dispersing, adding 0-25 parts of foaming agent, 2-14 parts of foam stabilizer and 0.1-8.5 parts of catalyst, and uniformly stirring;
(3) uniformly mixing the two solutions, adding 15-63 parts of isocyanate, uniformly stirring, injecting into a mold, and foaming and molding at room temperature; and baking and curing to obtain the radiation-resistant polyimide foam material for the ship.
The invention also provides the application of the radiation-resistant polyimide foam material in any one of the technical schemes, the radiation-resistant polyimide foam material in any one of the technical schemes or the radiation-resistant polyimide foam material prepared by the preparation method in any one of the technical schemes in the field of ships.
The radiation-resistant polyimide foam material for the ship contains cerium oxide particles, and the cerium oxide particles are compounded in porous polyimide foam in a specific form. According to the invention, through high shear force generated by ultrasonic cavitation, the environment-friendly cerium oxide particles with barrier and shielding effects on nuclear radiation are refined into nano-scale, and are compounded in the polyimide foam material through the processes of high-speed stirring, room-temperature forming, post-curing and the like, the outer layer empty orbit of rare earth ions and lone pair electrons or unshared pair electrons provided by N and/or O atoms in an imide ring are effectively combined to form a bonding effect, so that a specific compounding form combining physical compounding and chemical bonding is realized, and the irradiation resistance of the polyimide foam material is effectively improved. Compared with the traditional shielding material of heavy metals such as lead, tungsten, barium and the like with chemical toxicity, the cerium oxide can effectively improve the irradiation resistance of the polyimide foam material and has no threat to the environment. The cerium oxide can effectively improve the radiation resistance of the material, and mainly has the advantages that when radiation passes through the cerium oxide, a photoelectric effect, a Compton effect and an electron pair effect which can absorb or scatter radiation such as X rays and gamma rays can occur, so that the cerium oxide has the effect of blocking and shielding the radiation. The stable bonding effect formed by the effective combination of the outer layer hollow orbit of the rare earth ions and lone pair electrons or unshared pair electrons provided by N and O atoms in the imide ring can effectively ensure that cerium oxide is uniformly dispersed in a polyimide foam system, the dose-effect ratio is maximized, and the influence of the addition amount on the reduction of the overall performance is reduced.
The radiation-resistant polyimide foam material provided by the invention has the advantages of simple preparation process, easiness in control and contribution to realizing industrial continuous production, can effectively improve the radiation resistance of the marine polyimide foam material, and has important reference significance for improving the safety performance of nuclear power ships and meeting the environmental protection requirement.
Experimental results show that the mechanical properties of the irradiation-resistant polyimide foam provided by the invention are less affected after irradiation, the tensile strength is reduced by 11.1%, the tear strength is reduced by 10.5%, and the compressive strength is reduced by 11.7%, while the tensile strength, the tear strength and the compressive strength of the polyimide foam without cerium oxide particles are respectively reduced by 51.9%, 59% and 58.5%. It can be seen that the addition of cerium oxide particles improves the radiation resistance of the polyimide foam.
For further illustration of the present invention, the radiation-resistant polyimide foam material, the preparation method and the application thereof provided by the present invention will be described in detail with reference to the following examples, but it should be understood that the examples are carried out on the premise of the technical scheme of the present invention, and the detailed embodiments and the specific operation procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
Mixing 24 parts of PMDA and 30 parts of DMF according to a formula, heating, stirring and heating to 80 ℃, and reacting for 6 hours; mixing 5 parts of cerium oxide and 30 parts of water, ultrasonically dispersing for 15min at the power of 150W, adding 1.2 parts of methanol, 2 parts of polyether modified silicone oil and 0.5 part of metal catalyst, and uniformly stirring; and (3) uniformly mixing the two solutions, adding 40 parts of PM-400, stirring at 2000r/min for 12s, injecting into a mold, and foaming and molding at room temperature. And baking and curing for 5 hours at 220 ℃ to obtain the radiation-resistant polyimide foam material for the ship.
Example 2
Mixing 24 parts of PMDA and 30 parts of DMF according to a formula, heating, stirring and heating to 80 ℃, and reacting for 6 hours; mixing 10 parts of cerium oxide and 30 parts of water, ultrasonically dispersing for 15min at the power of 150W, adding 1.2 parts of methanol, 2 parts of polyether modified silicone oil and 0.5 part of metal catalyst, and uniformly stirring; and (3) uniformly mixing the two solutions, adding 40 parts of PM-400, stirring at 2000r/min for 12s, injecting into a mold, and foaming and molding at room temperature. And baking and curing for 5 hours at 220 ℃ to obtain the radiation-resistant polyimide foam material for the ship.
Example 3
Mixing 24 parts of PMDA and 30 parts of DMF according to a formula, heating, stirring and heating to 80 ℃, and reacting for 6 hours; mixing 15 parts of cerium oxide and 30 parts of water, ultrasonically dispersing for 15min at the power of 150W, adding 1.2 parts of methanol, 2 parts of polyether modified silicone oil and 0.5 part of metal catalyst, and uniformly stirring; and (3) uniformly mixing the two solutions, adding 40 parts of PM-400, stirring at 2000r/min for 12s, injecting into a mold, and foaming and molding at room temperature. And baking and curing for 5 hours at 220 ℃ to obtain the radiation-resistant polyimide foam material for the ship.
Comparative example 1
Mixing 24 parts of PMDA and 30 parts of DMF according to a formula, heating, stirring and heating to 80 ℃, and reacting for 6 hours; adding 30 parts of water, 1.2 parts of methanol, 2 parts of polyether modified silicone oil and 0.5 part of metal catalyst, and uniformly stirring; and (3) uniformly mixing the two solutions, adding 40 parts of PM-400, stirring at 2000r/min for 12s, injecting into a mold, and foaming and molding at room temperature. And baking and curing for 5 hours at 220 ℃ to obtain the polyimide foam material.
The performance of the irradiation-resistant polyimide foam material prepared in the embodiment of the invention and the performance of the polyimide foam material prepared in the comparative example are tested.
The data of the sample after irradiation is obtained by testing the sample after absorbing 10125Gy irradiation dose, and the irradiation source is60Co-gamma rays. The tensile strength test standard is GB/T6344-.
Referring to table 1, table 1 shows the performance test results of the radiation-resistant polyimide foam prepared in the inventive example and the polyimide foam prepared in the comparative example.
TABLE 1
Figure BDA0002809164630000151
As can be seen from the experimental data in Table 1, the addition of cerium oxide can keep the mechanical properties of the polyimide foam relatively stable, and only a small reduction is achieved, but the radiation resistance of the polyimide foam is greatly improved. The tensile strength of the sample without the addition of the cerium oxide is reduced by 51.9 percent after irradiation, and the tensile strength of the sample with the addition of 5 parts of the cerium oxide, 10 parts of the cerium oxide and 15 parts of the cerium oxide is reduced by 11.4 percent, 11.1 percent and 12 percent; the tearing strength of the sample without the cerium oxide is reduced by 59 percent after irradiation, and the tearing strength of the sample with 5 parts of cerium oxide, 10 parts of cerium oxide and 15 parts of cerium oxide is reduced by 13.3 percent, 12.3 percent and 10.5 percent; the compressive strength of the sample without the addition of cerium oxide was reduced by 58.5% after irradiation, and the compressive strength of the sample with the addition of 5 parts of cerium oxide, 10 parts of cerium oxide, and 15 parts of cerium oxide was reduced by 11.7%, 13.2%, and 12.8%. Therefore, the addition of cerium oxide significantly improves the radiation resistance of the polyimide foam.
While the present invention has been described in detail with respect to a radiation resistant polyimide foam for ships, its preparation and use, and while the principles and embodiments of the invention have been illustrated with specific examples, the above description is only intended to facilitate the understanding of the process and its core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims (10)

1. An irradiation-resistant polyimide foam material is characterized in that the irradiation-resistant polyimide foam material contains cerium oxide particles;
the irradiation-resistant polyimide foam material has a porous structure;
the cerium oxide particles are compounded in the polyimide foam.
2. The radiation-resistant polyimide foam material as claimed in claim 1, wherein the cerium oxide particles have a particle size of 0.5 to 4 μm;
the mass content of the cerium oxide particles is 5-15%;
the pore diameter of the porous structure is 100-700 mu m;
the combination mode of the cerium oxide and the polyimide comprises chemical bond bonding;
the radiation-resistant polyimide foam material comprises a radiation-resistant polyimide foam material for ships.
3. The radiation-resistant polyimide foam material as claimed in claim 1, wherein the radiation-resistant polyimide foam material has an open cell content of 80% to 99%;
the density of the radiation-resistant polyimide foam material is 9-12 kg/m3；
The cerium oxide particles are filled in the cell gaps, positioned in the cells and attached to the cell walls of the cells;
cerium ions in the cerium oxide are bonded with N and/or O atoms in an imide ring in a polyimide structure through coordination bonds;
the radiation-resistant polyimide foam material also comprises a foam stabilizer.
4. The radiation-resistant polyimide foam material is characterized by comprising the following raw materials in percentage by mass:
Figure FDA0002809164620000011
5. the radiation resistant polyimide foam of claim 4 wherein the isocyanate comprises one or more of PM-200, NE-466, PM-400, PM-700, 8122, 8214, and PM-8223;
the aromatic dianhydride comprises one or more of BTDA, PMDA and DSDA;
the solvent comprises one or more of DMSO, DMF, and DMAC;
the catalyst comprises a metal catalyst and/or an amine catalyst.
6. The radiation resistant polyimide foam material of claim 4, wherein the isocyanate has an isocyanate content of 28% to 35%;
the blowing agent comprises one or more of acetone, water, methanol, ethanol and 2-butoxyethanol;
the foam stabilizer comprises one or more of polyether modified silicone oil, silicone oil and water-soluble silicone oil;
the catalyst comprises one or more of dibutyltin dilaurate, stannous octoate, bismuth isooctanoate, N, N-dimethyl cyclohexylamine, N, N, N ', N ' -tetramethyl alkylene diamine and N, N ' -diethyl piperazine.
7. A method for preparing the radiation-resistant polyimide foam material as claimed in any one of claims 1 to 3 or the radiation-resistant polyimide foam material as claimed in any one of claims 4 to 6, comprising the steps of:
1) mixing aromatic dianhydride and a solvent to obtain a first solution;
mixing the cerium oxide, water, a foaming agent, a foam stabilizer and a catalyst again to obtain a second solution;
2) premixing the first solution and the second solution obtained in the step, finally mixing the premixed solution and isocyanate, then carrying out foaming molding in a mold, and finally curing to obtain the radiation-resistant polyimide foam material.
8. The method according to claim 7, wherein the mixing means includes heating and stirring;
the mixing temperature is 60-80 ℃;
the mixing speed is 300-500 r/min;
the mixing time is 6-12 h;
the means of remixing comprises ultrasonic mixing;
the power of ultrasonic mixing is 100-150W;
the remixing time is 10-15 min.
9. The method of claim 7, wherein the final mixing comprises high speed mixing;
the rotating speed of the final mixing is 1000-3000 r/min;
the final mixing time is 15-30 s;
the foaming and forming time is 15-20 min;
the curing temperature is 200-300 ℃;
the curing time is 4-8 h.
10. Application of the radiation-resistant polyimide foam material as defined in any one of claims 1 to 3, the radiation-resistant polyimide foam material as defined in any one of claims 4 to 6 or the radiation-resistant polyimide foam material prepared by the preparation method as defined in any one of claims 7 to 9 in the field of ships.
CN202011383778.7A 2020-11-30 2020-11-30 Radiation-resistant polyimide foam material and preparation method and application thereof Active CN112341815B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011383778.7A CN112341815B (en) 2020-11-30 2020-11-30 Radiation-resistant polyimide foam material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011383778.7A CN112341815B (en) 2020-11-30 2020-11-30 Radiation-resistant polyimide foam material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112341815A true CN112341815A (en) 2021-02-09
CN112341815B CN112341815B (en) 2023-09-22

Family

ID=74427311

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011383778.7A Active CN112341815B (en) 2020-11-30 2020-11-30 Radiation-resistant polyimide foam material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112341815B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101768362A (en) * 2010-01-12 2010-07-07 山东大学 Condensed room temperature vulcanized silicone rubber with radiation-resistant property and preparation method thereof
CN104592762A (en) * 2014-12-26 2015-05-06 中国科学院长春应用化学研究所 Radiation-resistant expandable fireproof material and preparation method thereof
CN111040161A (en) * 2019-12-30 2020-04-21 常州天晟新材料研究院有限公司 Heat-insulation polyimide foam material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101768362A (en) * 2010-01-12 2010-07-07 山东大学 Condensed room temperature vulcanized silicone rubber with radiation-resistant property and preparation method thereof
CN104592762A (en) * 2014-12-26 2015-05-06 中国科学院长春应用化学研究所 Radiation-resistant expandable fireproof material and preparation method thereof
CN111040161A (en) * 2019-12-30 2020-04-21 常州天晟新材料研究院有限公司 Heat-insulation polyimide foam material and preparation method thereof

Also Published As

Publication number Publication date
CN112341815B (en) 2023-09-22

Similar Documents

Publication Publication Date Title
Chen et al. Silicon oxide encapsulated ZIF-8 loaded on reduced graphene oxide to improve flame retardancy of waterborne epoxy coatings
CN105694665A (en) Flame-retardant coiled material and preparation method thereof
CN105001600B (en) A kind of preparation method of flame retardant epoxy foamed material
Sun et al. Superior flame retardancy and smoke suppression of epoxy resins with zinc ferrite@ polyphosphazene nanocomposites
CN111592813A (en) Intumescent fire-retardant coating and preparation method thereof
CN108034322A (en) A kind of fireproof coating and preparation method thereof
CN108715705A (en) A kind of water expansion heat-resistant fireproof fireproof coating and its preparation process
EP2883896A1 (en) Multifunctional epoxy resin with enhanced flame resistance
CN106046681B (en) A kind of flax fiber element base phosphorus expanding fire retardant and its preparation method and application
CN107629672A (en) A kind of waterproof polyurethane coating and preparation method thereof
CN109651787A (en) The SMC material of high fire-retardance, low-density
CN112679735A (en) Rigid polyimide foam material, and preparation method and application thereof
CN103589076A (en) Radiation-resistant halogen-free flame-retardant cable material and preparation method thereof
Hu et al. Structure‐thermal activity relationship in a novel polymer/MOF‐based neutron‐shielding material
CN110229304B (en) Flame-retardant graphene polyurethane composite foam material and preparation method thereof
CN112341815B (en) Radiation-resistant polyimide foam material and preparation method and application thereof
Qian et al. Improvement in alkali‐resistance of basalt fiber‐reinforced polymer by Ti3C2TX (MXene) modified matrix
Gao et al. Investigation of novel lightweight phenolic foam‐based composites reinforced with flax fiber mats
CN109503027B (en) Flame-retardant transparent concrete
CN112745502A (en) Flame-retardant wave-absorbing polyimide foam material and preparation method and application thereof
CN107418136A (en) A kind of composite foam insulation material and preparation method thereof
CN104356325B (en) Phenolic resin of nano layered silicate clay alteration and preparation method thereof
CN105820518A (en) Preparation method for modified polyol with ultrahigh temperature resistance and high flame resistance
Saltan et al. Preparation and characterization of novel boron containing nanocomposites with neutron radiation shielding properties
CN112441770A (en) Nano fireproof material for building and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20230206

Address after: No. 307, Building 6, No. 6 Qingyang Road, Xinbei District, Changzhou City, Jiangsu Province, 213125

Applicant after: Changzhou Fulong New Technology Materials Co.,Ltd.

Address before: 213125 No.6 Qingyang Road, Xuejia Town, Xinbei District, Changzhou City, Jiangsu Province

Applicant before: Jiangsu Zhongke polymer New Material Industry Technology Research Institute Co.,Ltd.

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant