CN116490557A - Polyimide composite powder containing silane agent and preparation method thereof - Google Patents

Polyimide composite powder containing silane agent and preparation method thereof Download PDF

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Publication number
CN116490557A
CN116490557A CN202080107336.1A CN202080107336A CN116490557A CN 116490557 A CN116490557 A CN 116490557A CN 202080107336 A CN202080107336 A CN 202080107336A CN 116490557 A CN116490557 A CN 116490557A
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composite powder
polyimide composite
silane agent
aminopropyl
powder according
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田珍硕
李吉男
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Polyimide Advanced Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—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
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The present invention relates to a polyimide composite powder containing a silane agent and a method for preparing the same, and more particularly, the method for preparing the polyimide composite powder comprises: step a) preparing a polyamic acid by containing dianhydride and diamine; and a step b) of imidizing by adding a silane agent to the polyamic acid prepared through the above step a). The present invention uses a silane agent in a specific ratio and aqueous polymerization, thereby improving fluidity and dispersibility without deteriorating mechanical properties.

Description

Polyimide composite powder containing silane agent and preparation method thereof
Technical Field
The present invention relates to a method for producing a polyimide composite powder containing a silane agent, and more particularly, to a polyimide composite powder and a method for producing the same, wherein the polyimide composite powder is produced by mixing a silane agent in a specific ratio and polymerizing the mixture in a water system, thereby imparting fluidity and dispersibility without deteriorating mechanical properties.
Background
The polymer molding involves a physical process for producing a molded article from a polymer material such as plastic or rubber, and includes a series of steps including shaping the polymer material in a predetermined shape by applying conditions such as heat and pressure, and shaping the polymer material in a liquid state without using heat or pressure. The molding process of the polymer material is classified into a first molding (injection, extrusion, hollow molding, etc.), a second molding (thermoforming, joining, etc.), etc. according to the steps, and classified into compression molding, calender molding, injection molding, vacuum molding, hollow molding, foam molding, fiber spinning, etc. according to the method. Polymer molding requires a product designed to have a predetermined quality and is price competitive, and even if the polymer has properties, it is difficult to directly manufacture a molded product having desired properties because various changes are caused by conditions such as heat and pressure during molding.
Polyimide is generally a high heat resistant polymer prepared by imidizing a tetracarboxylic acid or a derivative thereof and an aromatic diamine or an aromatic diisocyanate after polycondensation. The polyimide is insoluble in a solvent and is not melted by heating, and may have various molecular structures depending on the type of monomer used. In general, pyromellitic dianhydride (PMDA) or biphenyl tetracarboxylic dianhydride (BPDA) is used as an aromatic tetracarboxylic acid derivative component, and diaminodiphenyl ether (ODA) or p-phenylenediamine (p-PDA) is used as an aromatic diamine component, so that the preparation is carried out by polycondensation.
Polyimide has high heat resistance and high strength, and thus many studies have been conducted on its use in the fields of automobiles, aerospace, aviation, electric and electronic parts, and the like. Since polyimide is usually processed in a state of polyamide acid as a precursor because of insolubility and insolubility of imide ring in repeating units, polyimide modified or improved in heat resistance, alkali resistance, dimensional stability, low absorptivity and the like, for example, polyamide imide (polyamide imide), polyether imide and the like have been disclosed starting from wholly aromatic polyimide resin of Du Pont in 1962.
Polyimide resins can be prepared by relatively simple methods such as mechanical agitation, thermal imidization, etc. of polyimide monomers. However, in the molding process for producing a polyimide molded article, since the moldability and processability of a polyimide resin are very poor, it is difficult to produce a molded article by a processing apparatus for a general polymer. As an effort to overcome moldability and processability, attempts have been made to prepare molded articles from polyimide powders.
Polyimide powder is different from polyimide resin in morphology, and it is difficult to use a molding method such as heating and melting, which are generally known. Further, the preparation of molded articles from the powder is affected by various factors such as specific surface area, imidization degree, crystallization degree, molecular weight, particle size, etc. of the powder, and various conditions must be coordinated. Therefore, it is generally required to prepare a molded article from a polyimide resin and further study is made on preparing a molded article from a polyimide powder.
In connection with this, a polyimide powder and a polyimide molded body prepared from a mixture of 3,3', 4' -biphenyl tetracarboxylic dianhydride and pyromellitic dianhydride and a mixture of p-phenylene diamine (m-phenylene) and 4,4' -diaminodiphenyl ether are disclosed in U.S. patent No. 9,469,048, and a molded article prepared by dry mixing and compression molding polyimide microparticles formed by polymerization of aliphatic diamine and tetracarboxylic acid is disclosed in U.S. patent No. 7,758,781. Also, korean patent No. 1,987,511 discloses thermoplastic polyimide powders which are prepared from aliphatic diamines and aromatic tetracarboxylic acids and belong to semi-crystalline and semi-aromatic groups.
However, even if these efforts are made, polyimide powder is difficult to use as a material member because of its low dielectric properties, and molding and processing are difficult because of its low dispersibility, and there are problems that mechanical properties are deteriorated in solving the molding and processing problems.
Accordingly, the present inventors have made a finding that a polyimide composite powder is prepared by including a silane agent in the process of preparing a polyimide powder, and as a result, it has been confirmed that the polyimide composite powder has excellent mechanical strength and improved flowability and dispersibility, thereby completing the present invention.
Disclosure of Invention
Technical problem
The present invention aims to solve the problem that the conventional polyimide powder is difficult to mold due to low dispersibility and fluidity, and to solve the problem that the dispersibility cannot be improved or the mechanical properties cannot be maintained when other fillers are used to improve the dispersibility.
Technical proposal
The invention provides polyimide composite powder, which comprises polyimide powder and a silane agent, wherein the content of the silane agent is more than 0.1 weight percent relative to the total weight.
According to an example of the present invention, the content of the above-mentioned silane agent may be more than 0.1 weight percent and less than 20 weight percent with respect to the total weight.
According to an example of the present invention, the content of the above-mentioned silane agent may be 1 to 10 weight percent with respect to the total weight.
According to an embodiment of the present invention, the silane agent may be at least one selected from the group consisting of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3- (2-aminoethyl) aminopropyl trimethoxysilane, 3-phenylaminopropyl trimethoxysilane, 2-aminophenyl trimethoxysilane and 3-aminophenyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-glycidoxypropyl triethoxysilane and 3-glycidoxypropyl methylethoxysilane.
According to an embodiment of the present invention, the silane agent may be 3-aminopropyl trimethoxysilane or 3-aminopropyl triethoxysilane.
The invention also provides a preparation method of the polyimide composite powder, which comprises the following steps: step a) preparing a polyamic acid by containing dianhydride and diamine; and a step b) of imidizing by adding a silane agent to the polyamic acid prepared through the above step a).
The present invention also provides a polyimide molded article produced by sintering the polyimide composite powder.
According to an example of the present invention, the present invention is characterized in that in the above step a), the polyamic acid is prepared using distilled water as a solvent.
According to an example of the present invention, in the above step a), the stirring may be performed at a temperature of 0 to 150 ℃ and a pressure of 0.1 to 10bar for 5 minutes to 4 hours.
According to an example of the present invention, in the above step a), the dianhydride may be a dianhydride represented by the following chemical formula 1.
Chemical formula 1:
r in the above chemical formula 1 1 Selected from the group consisting of the following chemical structures:
and
According to an example of the present invention, in the above step a), the diamine may be a diamine represented by the following chemical formula 2.
Chemical formula 2:
in the above chemical formula 2, R 2 Selected from the group consisting of the following chemical structures:
and +.>
According to an example of the invention, in step b) above, the silane agent may be in a liquid state.
According to an example of the present invention, in the above step b), the silane agent may be one or more selected from the group consisting of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3- (2-aminoethyl) aminopropyl trimethoxysilane, 3-phenylaminopropyl trimethoxysilane, 2-aminophenyl trimethoxysilane and 3-aminophenyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-glycidoxypropyl triethoxysilane and 3-glycidoxypropyl methylethoxysilane.
According to a specific example of the present invention, in the above step b), the silane agent may be 3-aminopropyl trimethoxysilane or 3-aminopropyl triethoxysilane.
According to an example of the present invention, in the above step b), the content of the silane agent may be more than 0.1 weight percent and less than 20 weight percent with respect to the total weight of the polyamic acid and the silane agent.
According to an embodiment of the present invention, in the above step b), the content of the silane agent may be 1 to 10 weight percent with respect to the total weight of the polyamic acid and the silane agent.
According to an example of the present invention, in the above step b), the imidization may be stirring under a temperature condition of 150 to 400 ℃ and a pressure condition of 10 to 300bar for 5 minutes to 10 hours.
According to an example of the present invention, the present invention provides a polyimide composite powder prepared by the above-described preparation method, which can be prepared into a molded article by a process comprising sintering at a temperature of 100 to 550 ℃ for 1 to 5 hours.
According to an example of the present invention, the present invention is characterized in that the angle of repose of the above polyimide composite powder is less than 40 °.
According to an embodiment of the present invention, the polyimide composite powder can be used to prepare a molded article having a tensile strength of 50Mpa or more.
ADVANTAGEOUS EFFECTS OF INVENTION
The polyimide composite powder and the method for producing the same according to the present invention have the advantage of improving dispersibility of the polyimide powder and maintaining excellent mechanical properties by using a silane agent, unlike conventional fillers.
Detailed Description
Best Mode for Carrying Out The Invention
The present invention relates to a polyimide composite powder comprising a polyimide powder and a silane agent, the content of the silane agent being 1 to 10 weight percent relative to the total weight.
Mode for carrying out the invention
The present invention will be described in detail below.
The invention relates to polyimide composite powder, which comprises polyimide powder and a silane agent, wherein the content of the silane agent is more than 0.1 weight percent relative to the total weight.
Furthermore, the present invention relates to a method for preparing polyimide composite powder, comprising: step a) preparing a polyamic acid by containing dianhydride and diamine; and a step b) of imidizing by adding a silane agent to the polyamic acid prepared through the above step a).
The present invention also relates to a polyimide molded article produced by sintering the polyimide composite powder.
In the present invention, the silane agent means all kinds of silane compounds that can form interface control of polyimide powder with polyimide molecular structure by chemical bond or non-chemical bond. In the present invention, the method for obtaining the silane agent is not limited.
According to an example of the present invention, the content of the above-mentioned silane agent may be more than 0.1 weight percent and less than 20 weight percent with respect to the total weight.
Specifically, the content of the above silane agent may be 0.2 to 18 weight percent, 0.3 to 17 weight percent, 0.4 to 16 weight percent, 0.5 to 15 weight percent, 0.6 to 14 weight percent, 0.7 to 13 weight percent, 0.75 to 12.5 weight percent, 0.8 to 12 weight percent, 0.85 to 11.5 weight percent, 0.9 to 11 weight percent, 0.95 to 10.5 weight percent, 1 to 10 weight percent, relative to the total weight.
In the present invention, if the weight percentage of the silane agent is less than the above range, the angle of repose of the polyimide composite powder is more than 40 °, fluidity will not be improved, and molding problems remain, and if it is more than the above range, no dispersion and precipitate formation will occur due to aggregation between the silane agent and polyimide, and the tensile strength of the molded article will be significantly reduced due to deformation of the molecular structure.
According to an embodiment of the present invention, the silane agent may be in a liquid state.
According to an embodiment of the present invention, the silane agent is at least one selected from the group consisting of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3- (2-aminoethyl) aminopropyl trimethoxysilane, 3-phenylaminopropyl trimethoxysilane, 2-aminophenyl trimethoxysilane and 3-aminophenyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-glycidoxypropyl triethoxysilane and 3-glycidoxypropyl methylethoxysilane. The silane agent may be used alone or in combination of two or more thereof in a predetermined ratio.
According to a specific embodiment of the present invention, the silane agent is 3-aminopropyl trimethoxysilane or 3-aminopropyl triethoxysilane.
According to an embodiment of the present invention, the polyimide composite powder may be a wholly aromatic polyimide, a partially alicyclic polyimide, or a wholly alicyclic polyimide. However, the polyimide composite powder produced by the production method of the present invention has excellent effects of having fluidity and dispersibility and maintaining mechanical properties even when it is wholly aromatic.
According to an example of the present invention, the above polyimide composite powder may be prepared into a molded article by including a step of sintering at a temperature of 100 to 550 ℃ for 1 to 5 hours.
According to an example of the present invention, the present invention is characterized in that the angle of repose of the above polyimide composite powder is less than 40 °.
Further, according to an embodiment of the present invention, the polyimide composite powder can be produced into a molded article having a tensile strength of 50Mpa or more. According to an embodiment of the present invention, the polyimide composite powder can be prepared into a molded article having a tensile strength of 60Mpa or more.
According to an example of the present invention, the present invention is characterized in that in the above step a), the polyamic acid is prepared using distilled water as a solvent. In the present invention, the dissolution of the silane agent is facilitated by using distilled water as a solvent, and no waste solvent is generated after the preparation of the polyimide composite powder, so that no deterioration in mechanical properties is generated after the removal of the residual solvent.
In the present invention, the distilled water is not limited to distilled water in a literal sense, and any state of water such as deionized water and tap water may be used in addition to distilled water. The amount of distilled water may be appropriately adjusted according to the amounts of dianhydride and diamine.
According to an example of the present invention, in the above step a), 100 parts by weight of the dianhydride compound, 80 to 120 parts by weight of the diamine, and 1000 to 1200 parts by weight of the mixed solvent may be used to prepare the polyamic acid based on the dianhydride compound. Distilled water may be used as a solvent in the respective weight part ranges to form the monomer salt.
According to an example of the present invention, in the above step a), the stirring may be performed at a temperature of 0 to 150 ℃ and a pressure of 0.1 to 10bar for 5 minutes to 4 hours.
Specifically, in the above step a), the temperature may be 30 to 130 ℃, 50 to 120 ℃, 60 to 100 ℃. And, in the above step a), the pressure may be 0.2bar to 8bar, 0.3bar to 6bar, 0.5bar to 5bar. And, in the above step a), the time may be 10 minutes to 3.5 hours, 30 minutes to 3 hours. The polyamic acid salt can be prepared by directly producing no imidization under the conditions of temperature, pressure and time.
According to an example of the present invention, in the above step a), the dianhydride may be a dianhydride represented by the following chemical formula 1.
Chemical formula 1:
r in the above chemical formula 1 1 Selected from the group consisting of the following chemical structures:
and
According to an example of the present invention, in the above step a), the diamine may be a diamine represented by the following chemical formula 2.
Chemical formula 2:
/>
in the above chemical formula 2, R2 is selected from the group consisting of the following chemical structures:
/>
/>
/>
/>
/>
and +.>
According to an example of the invention, in step b) above, the silane agent may be in a liquid state.
According to an example of the present invention, in the above step b), the silane agent is one or more selected from the group consisting of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3- (2-aminoethyl) aminopropyl trimethoxysilane, 3-phenylaminopropyl trimethoxysilane, 2-aminophenyl trimethoxysilane and 3-aminophenyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-glycidoxypropyl triethoxysilane and 3-glycidoxypropyl methylethoxysilane. The silane agent may be used alone or in combination of two or more thereof in a predetermined ratio.
According to a specific example of the present invention, in the above step b), the silane agent is 3-aminopropyl trimethoxysilane or 3-aminopropyl triethoxysilane.
Also, according to an example of the present invention, in the above step b), the content of the silane agent may be more than 0.1 weight percent and less than 20 weight percent with respect to the total weight of the polyamic acid and the silane agent.
Specifically, the content of the silane agent is 0.2 to 18 weight percent, 0.3 to 17 weight percent, 0.4 to 16 weight percent, 0.5 to 15 weight percent, 0.6 to 14 weight percent, 0.7 to 13 weight percent, 0.75 to 12.5 weight percent, 0.8 to 12 weight percent, 0.85 to 11.5 weight percent, 0.9 to 11 weight percent, 0.95 to 10.5 weight percent, 1 to 10 weight percent, relative to the total weight of the polyamic acid and the silane agent.
In the present invention, a silane additive may be added in a polyamic acid salt state to change the structure of a polymer. Furthermore, the silane agent can have excellent properties in terms of angle of repose, dispersibility, mechanical properties, and the like by maintaining a predetermined ratio during the preparation of the polyimide composite powder.
According to an example of the present invention, in the above step b), the imidization may be performed under a temperature condition of 150 to 400 ℃ and a pressure condition of 10 to 300bar for 5 minutes to 10 hours.
Specifically, in the above step b), the temperature may be 160 to 250 ℃, 170 to 240 ℃, 180 to 220 ℃. If the reaction temperature is less than 150 ℃, the reaction rate is too low, and if the reaction temperature is more than 400 ℃, thermal decomposition of the monomer or polymer may occur.
And, in the above step b), the pressure may be 10bar to 300bar, 10bar to 100bar, 10bar to 80bar. If the reaction pressure is less than 10bar, it is difficult to control the reactivity, and if the reaction pressure is more than 300bar, it is difficult to obtain a polyimide composite powder having a high molecular weight.
And, in the above step b), the time may be 10 minutes to 10 hours, 10 minutes to 5 hours. If the reaction time is less than 5 minutes, the reaction is not satisfactory, and if the reaction time is more than 10 hours, hydrolysis of the polymer may occur.
Also, in the present invention, the polyimide composite powder may be prepared further including a filtration and drying step after the above step b).
The polyimide composite powder prepared according to an embodiment of the present invention may be prepared into a molded article by compression molding, spray molding, slush molding, hollow molding, extrusion molding, or spinning methods by including the above-described step of performing sintering.
Further, the polyimide composite powder prepared according to an embodiment of the present invention has improved moldability and tensile strength, and thus can be used in various industrial fields such as aerospace, electric/electronic, semiconductor, transparent/flexible display, liquid crystal back film, automobile, precision equipment, packaging, medical materials, separation film, fuel cell, and secondary battery.
Hereinafter, the method for producing the polyimide composite powder of the present invention and the physical properties of the polyimide composite powder produced by the production method will be described by way of examples. However, the present invention is not limited to the following examples.
< example 1> preparation of polyimide composite powder containing silane agent
After 255g of distilled water was charged into a 5-port beaker-type reaction vessel and the amount was measured, 23.46g of pyromellitic dianhydride (pyromellitic dianhydride, PMDA) was added thereto and dissolved by stirring with a high-speed stirrer to convert the mixture into a tetracarboxylic acid (tetracarboxylic acid) (70 ℃ C., 1 hour). Thereafter, 21.54g of 4,4' -Oxydianiline (ODA) was added to perform a reaction at a temperature of 70 ℃ for 2 hours, thereby synthesizing a monomer salt. In this case, the concentration of the monomer salt was 15 weight percent, and the solid content was 15 weight percent.
To the resulting mixture of monomer salts was added 0.45g of the silane agent aminopropyl triethoxysilane (Aminoppropyltrithioxirane) in powder form, the pressure in the high temperature and high pressure reactor was set to 12-15bar, and the mixture was stirred at 190℃for 6 hours. Thereafter, the polyimide composite powder suspension was washed with distilled water and subjected to reduced pressure filtration, thereby obtaining a polyimide composite powder.
< example 2> preparation of polyimide composite powder containing silane agent
A polyimide composite powder was prepared in the same manner as in example 1 above, except that 2.37g of the silane agent was used.
< example 3> preparation of polyimide composite powder containing silane agent
A polyimide composite powder was prepared in the same manner as in example 1 above, except that 5.00g of a silane agent was used.
Comparative example 1> preparation of polyimide powder
In the case where the silane agent was not contained, polyimide powder was prepared in the same manner as in example 1 described above.
Comparative example 2 preparation of polyimide composite powders having different silane agent contents
A polyimide composite powder was prepared in the same manner as in example 1 above, except that 0.045g of the silane agent was used.
Comparative example 3 preparation of polyimide composite powders having different silane agent contents
A polyimide composite powder was prepared in the same manner as in example 1 above, except that 11.25g of the silane agent was used.
< evaluation >
The angle of repose was measured by dropping the polyimide composite powder or polyimide powder prepared in examples 1 to 3 and comparative examples 1 to 3 above from a predetermined height onto a horizontal substrate using a powder tester (PT-X) to measure the angle of the resulting deposit.
The dispersibility of the polyimide composite powder or the polyimide powder prepared in examples 1 to 3 and comparative examples 1 to 3 was confirmed by placing the powder in water and stirring the powder with a magnetic stirrer for 3 minutes or longer.
Then, each 2g of the polyimide composite powder or polyimide powder prepared in examples 1 to 3 and comparative examples 1 to 3 was compression molded under a pressure of 96000psi using an ASTM D1708-specification test piece mold, and then heated and sintered under a nitrogen atmosphere at a temperature of 100 ℃ for 1 hour, at a temperature of 250 ℃ for 1 hour, and at a temperature of 450 ℃ for 1 hour, to prepare 10 test pieces. The tensile strength of the test piece prepared by the above procedure was measured to be shown in Table 1. Tensile strength of the test piece was measured according to ASTM D1708 using 5564UTM from instron.
TABLE 1
As shown in table 1, it was confirmed that the polyimide composite powders prepared according to examples 1 to 3 of the present invention increased the flowability of the powders by making the angle of repose smaller than 40 °. Further, it was confirmed that excellent molded articles can be produced because of the excellent dispersibility and the tensile strength of 50MPa or more and the almost no decrease in mechanical strength.
In comparative example 1 containing no silane agent and comparative example 2 containing 0.1 weight percent of silane agent, the angle of repose was 40 ° or more, the flowability of the powder was not improved, and in comparative example 3 containing 20 weight percent of silane agent, the angle of repose was less than 40 °, but the dispersibility was lowered, and a precipitate was formed, and since the tensile strength was less than 50Mpa, a molded article having poor mechanical properties was produced.
Therefore, the method for producing a polyimide composite powder according to the present invention imparts flow characteristics to a polyimide composite powder by adding a silane agent in the state of a monomer salt that is an intermediate step in the production step of the polyimide composite powder. In addition, excellent properties of improving fluidity and dispersibility are provided while maintaining excellent mechanical strength by adjusting the amount of the silane agent added. In addition, the reaction temperature is low, the reaction time is short, the efficiency in the preparation process is high, and the water is used as a reaction solvent, so that the method is environment-friendly and has the effect of reducing the cost.
Industrial applicability
The present invention can provide a polyimide composite powder having improved flow characteristics, mechanical strength, and dispersibility with the content of a specific silane agent. Therefore, the powder is effectively used to provide a molded article.

Claims (21)

1. A polyimide composite powder comprising a polyimide powder and a silane agent, wherein the silane agent is present in an amount of greater than 0.1 weight percent relative to the total weight.
2. The polyimide composite powder according to claim 1, wherein the content of the silane agent is more than 0.1% by weight and less than 20% by weight with respect to the total weight.
3. The polyimide composite powder according to claim 1, wherein the silane agent is contained in an amount of 1 to 10% by weight relative to the total weight.
4. The polyimide composite powder according to claim 1, wherein the silane agent is in a liquid state.
5. The polyimide composite powder according to claim 1, wherein the silane agent is at least one selected from the group consisting of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3- (2-aminoethyl) aminopropyl trimethoxysilane, 3-phenylaminopropyl trimethoxysilane, 2-aminophenyl trimethoxysilane and 3-aminophenyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-glycidoxypropyl triethoxysilane and 3-glycidoxypropyl methylethoxysilane.
6. The polyimide composite powder according to claim 1, wherein the silane agent is 3-aminopropyl trimethoxysilane or 3-aminopropyl triethoxysilane.
7. The polyimide composite powder according to claim 1, wherein the polyimide composite powder can be prepared into a molded article by a process comprising sintering at a temperature of 100 ℃ to 550 ℃ for 1 hour to 5 hours.
8. The polyimide composite powder according to claim 1, wherein the angle of repose of the polyimide composite powder is less than 40 °.
9. The polyimide composite powder according to claim 1, wherein the polyimide composite powder can be produced into a molded article having a tensile strength of 50Mpa or more.
10. A method for preparing polyimide composite powder, comprising the steps of:
step a) preparing a polyamic acid by containing dianhydride and diamine; and
step b) of imidizing by adding a silane agent to the polyamic acid prepared through step a) above.
11. The method for producing a polyimide composite powder according to claim 10, wherein in the step a), the polyamic acid is produced using distilled water as a solvent.
12. The method for preparing a polyimide composite powder according to claim 10, wherein in the step a), the mixture is stirred at a temperature of 0 to 150 ℃ and a pressure of 0.1 to 10bar for 5 minutes to 4 hours.
13. The method for producing a polyimide composite powder according to claim 10, characterized in that,
in the above step a), the dianhydride is a dianhydride represented by the following chemical formula 1:
chemical formula 1:
r in the above chemical formula 1 1 Selected from the group consisting of the following chemical structures:
14. the method for producing a polyimide composite powder according to claim 10, wherein in the step a), the diamine is a diamine represented by the following chemical formula 2:
chemical formula 2:
in the above chemical formula 2, R 2 Selected from the group consisting of the following chemical structures:
and +.>。
15. The method for producing a polyimide composite powder according to claim 10, wherein in the step b), the silane agent is in a liquid state.
16. The method according to claim 10, wherein in the step b), the silane agent is at least one selected from the group consisting of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldimethoxy silane, 3-aminopropyl methyldiethoxy silane, 3- (2-aminoethyl) aminopropyl trimethoxysilane, 3-phenylaminopropyl trimethoxysilane, 2-aminophenyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-glycidoxypropyl triethoxysilane, and 3-glycidoxypropyl methylethoxy silane.
17. The method for producing a polyimide composite powder according to claim 10, wherein in the step b), the silane agent is 3-aminopropyl trimethoxysilane or 3-aminopropyl triethoxysilane.
18. The method for producing a polyimide composite powder according to claim 10, wherein in the step b), the content of the silane agent is more than 0.1% by weight and less than 20% by weight relative to the total weight of the polyamic acid and the silane agent.
19. The method for producing a polyimide composite powder according to claim 10, wherein in the step b), the content of the silane agent is 1 to 10% by weight relative to the total weight of the polyamic acid and the silane agent.
20. The method for preparing polyimide composite powder according to claim 10, wherein in the above step b), imidization is performed under a temperature condition of 150 to 400 ℃ and a pressure condition of 10 to 300bar for 5 minutes to 10 hours.
21. A polyimide molded article characterized by being produced by comprising the step of sintering the polyimide composite powder according to any one of claims 1 to 9.
CN202080107336.1A 2020-11-30 2020-12-28 Polyimide composite powder containing silane agent and preparation method thereof Pending CN116490557A (en)

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US20050215715A1 (en) 2003-12-19 2005-09-29 Schmeckpeper Mark R Blends of high temperature resins suitable for fabrication using powdered metal or compression molding techniques
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