CN113493566A - End-capping reagent for preparing polyimide material, polyimide material and preparation method thereof - Google Patents
End-capping reagent for preparing polyimide material, polyimide material and preparation method thereof Download PDFInfo
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- CN113493566A CN113493566A CN202110884856.XA CN202110884856A CN113493566A CN 113493566 A CN113493566 A CN 113493566A CN 202110884856 A CN202110884856 A CN 202110884856A CN 113493566 A CN113493566 A CN 113493566A
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- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- 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
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
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- 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
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1017—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)amine
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- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C09D179/085—Unsaturated polyimide precursors
Abstract
The present disclosure provides a method for preparing a polyimide material, comprising the steps of: (1) adding a certain amount of solvent into a reactor in advance, adding a certain proportion of diamine and tetracarboxylic dianhydride into the reactor, and mechanically stirring for 1-72 h to ensure that the diamine and the tetracarboxylic dianhydride are fully subjected to polymerization reaction to generate polyamic acid; (2) after the reaction is completed, adding an end-capping reagent A, wherein the molar ratio of the addition amount of the end-capping reagent A to the diamine is 0.001-0.2, so that the end-capping reagent A fully reacts with the end group of the polyamic acid to obtain the polyamic acid varnish; (3) and coating the polyamic acid varnish on a substrate to be cured into polyimide. The phenylethynyl end capping agent A disclosed by the invention has an aromatic structure, and limits the thermal decomposition of a high-molecular end group, so that the end-capped polyimide has good thermal stability, the thermal decomposition temperature of a polyimide material is increased, and the application temperature range of the polyimide material is further expanded.
Description
Technical Field
The disclosure relates to the field of materials, and in particular relates to a blocking agent for preparing a polyimide material, the polyimide material and a preparation method thereof.
Background
Polyimides are a class of polymeric materials in which the repeating units are linked by imide rings. The aromatic polyimide is wholly aromatic polyimide consisting of aromatic dianhydride and aromatic diamine. Is one of the engineering plastics with the best heat resistance in the current high polymer materials. Due to its outstanding physicochemical properties including thermal stability, solubility resistance, excellent insulating properties and radiation resistance, polyimides are widely used in the fields of aerospace, microelectronics, liquid crystals, separation membranes and the like. In recent years, with the development of display field, the PI which is light and flexible is considered as a kind of flexible substrate material with great application potential. The formula (1) is a general formula of a polyimide molecular structure.
In the formula (1), X is a tetravalent group, and Y is a divalent group.
With the rapid development of microelectronic technology, core technologies represented by integrated circuits enter a new stage. Nowadays, the microelectronic technology has become the foundation for supporting the development of society, and is one of the important indexes for measuring the national competitiveness. Since the first ic appeared in 1958, large-scale and very large-scale integrated circuit technology has been developed, and the integration level has been improved by 9 orders of magnitude. The traditional through hole insertion technology has low requirement on the thermal dimensional stability of the substrate, and the stress between the substrate and the component is buffered through a lead. With the widespread use of the new-generation microelectronic technologies represented by surface mount technology, the pitch of the devices is reduced to 1mm, the line width is measured in nanometers, and the stress is directly borne by the devices due to the absence of the buffer effect of the leads. Thus, higher microelectronics technologies require a material compatible therewith as a support. The research on the polyimide film with matched thermal expansion coefficients can reduce the influence of stress on components and parts, prolong the service life and provide material support for developing more advanced microelectronic technology.
The Coefficient of Thermal Expansion (CTE) is one of the basic physical parameters of a material, is an important index for representing the Thermal stability of the material, and is an important parameter in the fields of chemical industry, machinery, microelectronics, energy sources and the like. For products such as printed circuit boards, photosensitive films, solar panels, display panels and the like, the CTE of the material not only influences the service performance, but also is a key parameter for structural design and process research.
In the case of printed circuit board substrates, CTE is one of the important performance criteria. The components with different properties are fixed on the surface of the circuit board through a proper assembly process to form an electronic product with certain functions. Through-hole mounting technology requires less substrate CTE, and stresses between the substrate and the component are buffered by the leads. The surface mounting technology can obviously improve the assembly density and reduce the volume and weight of electronic products, the size of the components is only about 10 percent of that of the traditional plug-in components, the volume of the electronic products is only about 50 percent of that of the traditional process, the weight is only about 30 percent, and the cost is reduced by about 50 percent. But the stress is directly borne by the element due to the absence of the cushioning effect of the leads. The polyimide film with matched CTE can avoid warping in the process of processing and using, and provides effective protection for components and circuits and prolongs the service life. For example, for polyimide applications in flexible printed circuit boards, the CTE requirement is in the range of 16-22 ppm/deg.C, while the CTE of polyimide materials used in OLED displays is less than 8 ppm/deg.C.
To control the CTE of polyimide, the main methods can be divided into: 1) inorganic filler modification, 2) molecular structure design and 3) blending modification. Conventionally, it has been proposed to obtain a film having a low linear expansion coefficient and high transparency by adding a tetracarboxylic dianhydride having a specific structure as a polymerization monomer (patent document 1: CN 112334521A); there have also been proposed a method in which a compound containing an alkali metal or an alkaline earth metal is mixed with a polyamic acid and imidized to improve the transparency and heat resistance of the obtained polyimide film or to reduce the coefficient of linear expansion (patent document 2: WO 2009/069688); it has also been proposed to reduce the linear expansion coefficient and the retardation in the thickness direction of a polyimide film by using a polyimide having a naphthalene structure and a fluorene structure (patent document 3: WO 2014/162734).
In recent years, the use of polyimide films for substrates for TFT matrices has been studied. The TFT matrix is fabricated through a process using polycrystalline Low Temperature Polysilicon (LTPS). Therefore, polyimide films used for substrates for TFT matrices are required to have higher heat resistance, higher bending strength, and excellent flexibility than conventional polyimide films. However, these properties are not sufficient in the polyimide film of any of the above documents, and it is required to improve heat resistance and bending strength and further improve flexibility while reducing retardation and linear expansion coefficient in the thickness direction.
In an AMOLED (Active-matrix organic light-emitting diode) manufacturing process, a subsequent vapor deposition process has severe requirements on gas components in a chamber, and gas released from Polyimide (PI) may adversely affect the performance of a deposited film. On the other hand, the gas released from the material at high temperature affects the function of the device, and in severe cases, corrodes the production equipment. Therefore, it is important to increase the thermal decomposition temperature (Td) and the glass transition temperature (Tg) of polyimide and widen the processing window.
On the other hand, studies have shown that the stress between the substrate and the device is proportional to the difference in CTE between the two, and that an excessive difference can lead to device detachment. Therefore, materials should be selected to match as closely as possible their CTE, with differences of less than 2 ppm/deg.C typically being required. Polyimide films have been widely used in microelectronic devices, but because the CTE of polyimide and the CTE of the device are not matched, the polyimide films may warp during processing and use, which may affect the service life of the devices. In addition, high-precision equipment such as a thin film type optical telescope requires the difference to be 0ppm, which limits the application field of polyimide materials.
Disclosure of Invention
In order to solve the problem that the CTE of the current polyimide material is matched with the CTE of other materials, the technical scheme adopted by the invention is as follows:
the invention provides a method for flexibly adjusting the CTE of a polyimide material by adding a blocking agent A containing a benzene ring and adjusting the amount of the blocking agent A under the condition of no special requirements on reaction equipment and reaction conditions. The operation steps are as follows: adding a certain amount of solvent into a reactor, then adding a certain proportion of diamine component and tetracarboxylic dianhydride, fully stirring for reaction, adding a certain amount of end-capping agent A, and continuously stirring until the reaction is complete to obtain the polyamic acid varnish (polyimide precursor, also called polyimide slurry). After the reaction is finished, a polyimide material (here, a polyimide film is taken as an example) can be obtained through a curing process.
The present disclosure provides a method for preparing a polyimide material, comprising the steps of:
(1) adding a certain amount of solvent into a reactor in advance, adding a certain proportion of diamine and tetracarboxylic dianhydride into the reactor, and mechanically stirring for 1-72 h to ensure that the diamine and the tetracarboxylic dianhydride are fully subjected to polymerization reaction to generate polyamic acid;
(2) after the reaction is completed, adding an end-capping reagent A, wherein the molar ratio of the addition amount of the end-capping reagent A to the diamine is 0.001-0.2, so that the end-capping reagent A and the end group of the polyamic acid are fully reacted to obtain the polyamic acid varnish;
(3) and coating the polyamic acid varnish on a substrate to be cured into polyimide.
Wherein, the structure of the blocking agent A is shown as follows, and can be described as follows: a phenylacetylene compound containing one carboxylic anhydride group or amino group. The carboxylic anhydride group or the amino group is directly linked to the benzene ring. The other groups attached to the benzene ring are not particularly limited, and the group R attached to the alkynyl group is H, or an alkyl group, or an aryl group, and R is preferably an alkyl group of H, C4-C8 or an aryl group of C8-C14.
Wherein, if the tetracarboxylic dianhydride: if the molar ratio of the diamine is less than 1, the end-capping agent A is a compound of formula A or formula B containing an anhydride structure; if the tetracarboxylic dianhydride: if the molar ratio of diamine is greater than 1, the blocking agent A is a compound of formula C containing an amino structure. The terminal group of the polyamic acid obtained after polymerization may be an amino group or an acid anhydride depending on the molar ratio of dianhydride to diamine, and different capping agents a are selected accordingly. The end-capping reagent A specifically selects phenylacetylene containing amino or acid anhydride, and the function of the end-capping reagent A is to react with the end group of the polyamic acid. In the compounds represented by the formula A, B and C, when R is a group with a small molecular weight, the molecular steric effect is small, the acetylene group is more likely to generate a crosslinking reaction at a high temperature, and the effect of improving the thermal stability (such as CTE and Tg) of the cured polyimide material is more obvious.
In a preferred embodiment, the reaction temperature is from 0 to 80 ℃ and preferably from 20 to 50 ℃.
In a preferred embodiment, the blocking agent A is added in a molar ratio to diamine of from 0.01 to 0.1.
Process for producing polyimide
The specific polyimide can be obtained by polymerizing a diamine component and a tetracarboxylic dianhydride component by a known method. The kinds of the diamine component and the tetracarboxylic dianhydride are not particularly limited.
The diamine component used in the production of the polyamic acid may contain only one component, or may contain two or more components.
The diamine may comprise, for example, p-phenylenediamine (PPD), m-phenylenediamine (MPD), 4 '-diaminodiphenyl ether (ODA), p-methylenedianiline (pMDA), m-methylenedianiline (mMDA), 1, 3-bis (3-aminophenoxy) benzene (133APB), 1, 3-bis (4-aminophenoxy) benzene (134APB), bis (trifluoromethyl) benzidine (TFDB), 2' -bis [4 (4-aminophenoxy) phenyl ] hexafluoropropane (4BDAF), 2 '-bis (3-aminophenyl) hexafluoropropane (33-6F), 2' -bis (4-aminophenyl) hexafluoropropane (44-6F), bis (4-aminophenyl) sulfone (4DDS), bis (3-aminophenyl) sulfone (3) DDS, 1, 3-cyclohexanediamine (13CHD), 1, 4-cyclohexanediamine (14CHD), 2 '-bis [4- (4-aminophenoxyphenyl) ] propane (6HMDA), 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (DBOH), 4' -bis (3-aminophenoxy) diphenylsulfone (DBSDA), 9-bis (4-aminophenyl) Fluorene (FDA), 9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA) and the like, but are not limited thereto. The diamine is preferably p-phenylenediamine (PPD), m-phenylenediamine (MPD), 4' -diaminodiphenyl ether (ODA), p-methylenedianiline (pMDA), m-methylenedianiline (mMDA), 1, 3-bis (3-aminophenoxy) benzene (133APB), 1, 3-bis (4-aminophenoxy) benzene (134APB), bis (trifluoromethyl) benzidine (TFDB), bis (4-aminophenyl) sulfone (4DDS), bis (3-aminophenyl) sulfone (3DDS), 1, 3-cyclohexanediamine (13CHD), 1, 4-cyclohexanediamine (14 CHD).
The tetracarboxylic dianhydride used for the preparation of the polyamic acid may contain only one component, or may contain two or more components.
The tetracarboxylic dianhydrides may include, for example, 3,3,4, 4-biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride (TDA), 3,3,4, 4-benzophenonetetracarboxylic dianhydride (BTDA), 4,4' -Oxydiphthalic Dianhydride (ODPA), bis (3, 4-dicarboxyphenyl) dimethylsilane dianhydride (SiDA), 4, 4-bis (3, 4-dicarboxyphenoxy) diphenyl sulfide dianhydride (BDSDA), sulfonyldiphthalic anhydride (SO2DPA), cyclobutanetetracarboxylic dianhydride (CBDA), 4,4'- (4, 4' -isopropyldiphenoxy) bis (phthalic anhydride) (6HBDA), and the like, but is not limited thereto. The tetracarboxylic acid dianhydride is preferably 3,3,4, 4-biphenyltetracarboxylic acid dianhydride (BPDA), pyromellitic acid dianhydride (PMDA), 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 3,4, 4-benzophenonetetracarboxylic acid dianhydride (BTDA), 4,4' -oxydiphthalic acid dianhydride (ODPA).
The polyimide film of the present invention can be obtained by:
1) polymerizing the diamine component and the tetracarboxylic dianhydride component to prepare polyamic acid;
2) coating a varnish containing the polyamic acid on a substrate to form a coating film;
3) the polyamic acid in the coating film is imidized (ring-closed).
Preparation of Polyamic acid
The tetracarboxylic dianhydride component and the diamine component are mixed and polymerized to obtain the polyamic acid. Here, the ratio (y/x) of the total molar amount y of the tetracarboxylic dianhydride component to the total molar amount x of the diamine component in the production of the polyamic acid is preferably 0.7 to 1.3, more preferably 0.8 to 1.2, and particularly preferably 0.9 to 1.1.
The method of polymerizing the diamine component and the tetracarboxylic dianhydride component is not particularly limited, and a known method can be used.
The solvent used in the production of the polyamic acid is not particularly limited as long as it can dissolve the diamine component and the tetracarboxylic dianhydride component. For example, an aprotic polar solvent and/or a water-soluble alcohol solvent can be used.
Examples of the aprotic polar solvent include: n-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, 1, 3-dimethyl-2-imidazolidinone, and the like; examples of the ether compound include 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, tetrahydrofurfuryl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, tetraethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, polyethylene glycol, polypropylene glycol, tetrahydrofuran, dioxane, 1, 2-dimethoxyethane, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.
Examples of the water-soluble alcohol-based solvent include: methanol, ethanol, 1-propanol, 2-propanol, t-butanol, ethylene glycol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 5-pentanediol, 2-butene-1, 4-diol, 2-methyl-2, 4-pentanediol, 1,2, 6-hexanetriol, diacetone alcohol, and the like.
The solvent used in the production of the polyamic acid may contain only one kind of the above-mentioned components, or may contain two or more kinds thereof. The solvent used for producing the polyamic acid is preferably N, N-dimethylacetamide, N-methyl-2-pyrrolidone, or a mixture thereof.
The polyamic acid is dissolved in a solvent to form a polyamic acid varnish. The varnish containing the polyamic acid (or block polyamic acid imide) and a solvent is prepared into a required form by coating, spinning and the like. Among them, the coated substrate is not particularly limited. The solvent contained in the varnish may be the same as or different from the solvent used in the preparation of the polyamic acid. The varnish may contain only one kind of solvent, or may contain two or more kinds.
The amount of the polyamic acid is preferably 1 to 50% by mass, and more preferably 10 to 25% by mass, based on the total amount of the polyamic acid varnish. If the amount of polyamic acid (or block polyamic acid imide) exceeds 50 mass%, the viscosity of the varnish becomes too high, and it may be difficult to coat the varnish on a substrate. On the other hand, if the concentration of the polyamic acid (or block polyamic acid imide) is less than 1 mass%, the viscosity of the varnish becomes too low, and the varnish may not be applied to a desired thickness in some cases. In addition, the drying of the solvent takes time, and the efficiency of producing the polyimide film is lowered.
The substrate to which the varnish is applied is not particularly limited as long as it has solvent resistance and heat resistance. The substrate is preferably a substrate having good releasability of the obtained polyimide layer, and is preferably a flexible substrate formed of glass, metal, a heat-resistant polymer film, or the like. Examples of flexible substrates formed from metal include: a metal foil formed of copper, aluminum, stainless steel, iron, silver, palladium, nickel, chromium, molybdenum, tungsten, zirconium, gold, cobalt, titanium, tantalum, zinc, lead, tin, silicon, bismuth, indium, or an alloy thereof. The surface of the metal foil may be coated with a release agent.
The method for applying the varnish to the substrate is not particularly limited as long as the substrate can be coated with the varnish in a constant thickness. Examples of the coating device include: die coaters, curtain coaters, spray coaters, and the like. The thickness of the coating film to be formed can be appropriately selected depending on the desired thickness of the polyimide film.
Imidization of polyamic acids
Subsequently, the coating film of the varnish containing the polyamic acid (or block polyamic acid imide) is cured to imidize (ring-close) the polyamic acid (or block polyamic acid imide). The specific method may be thermal or chemical. The specific additives used in the curing process and the temperature rising process are not particularly limited.
The beneficial effect of this disclosure:
both the CTE and Tg of the high molecular polymer are related to the motion state of the molecular chain of the high molecular polymer. According to the invention, a phenylacetylene compound containing a carboxylic acid anhydride group or amino is used as a blocking agent, and the blocking agent A with phenylethynyl can generate a crosslinking reaction to generate a conjugated polyene and a ring structure, so that the movement of a molecular chain of a high polymer is limited, and thus the CTE of a polyimide material can be reduced by adding the blocking agent A, so that the CTE of the polyimide material is more matched with a substrate material, and the Tg of the polyimide can be improved. In addition, Td is greatly affected by the terminal structure of the polymer. The end capping agent A has an aromatic structure, and limits the thermal decomposition of a high-molecular end group, so that the phenylethynyl end-capped polyimide has good thermal stability, the thermal decomposition temperature of the polyimide material is increased, and the application temperature range of the polyimide material is expanded.
The end capping agent A is adopted as the end capping agent, and the end capping agent has good compatibility with different anhydride and diamine monomers. The end capping agent A is combined with the end group of the polyamic acid to inhibit the decomposition of the end group and improve the thermal stability (thermal decomposition temperature T) of the polyimided). Different CTEs can be achieved by flexibly adjusting the amount of capping agent a.
The method provided by the disclosure is simple and easy to implement, and has no special requirements on equipment and reaction conditions; the application range is wide, the structures of the end-capping reagent and the monomer can be flexibly adjusted according to actual needs, and other properties of the polyimide, such as tensile strength, tensile modulus and the like, are not influenced.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the disclosure and together with the description serve to explain the principles of the disclosure.
Fig. 1 is a schematic diagram showing one embodiment of a method for synthesizing polyimide (taking PPD and BPDA as polymerization monomers as an example).
FIG. 2 is a schematic diagram showing another embodiment of a method for synthesizing polyimide (taking 4-PEPA as an example of a capping agent).
Detailed Description
The present disclosure will be described in further detail with reference to the drawings and embodiments. It is to be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limitations of the present disclosure. It should be further noted that, for the convenience of description, only the portions relevant to the present disclosure are shown in the drawings.
It should be noted that the embodiments and features of the embodiments in the present disclosure may be combined with each other without conflict. The present disclosure will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
The abbreviations of tetracarboxylic dianhydride and diamine are as follows:
s-BPPD: 3,3',4,4' -biphenyltetracarboxylic dianhydride.
And (3) PMDA: pyromellitic dianhydride.
PPD (p): p-phenylenediamine.
4,4' -ODA: 4,4' -diaminodiphenyl ether.
4-PEPA 4-phenylethynyl phthalic anhydride with the structural formula
4-isobutyl ethynyl phthalic anhydride with the structural formula
3-EA: 3-ethynylaniline with the structural formula
Examples
Comparative example 1A:
under N2 atmosphere, PPD and BPPD were mixed at a ratio of 1: a reaction was carried out at a molar ratio of 0.98 in a DMAc solvent at 50 ℃ for 5 hours to obtain a polyamic acid (PAA) solution having a solid content (mass) of 15%. The PAA solution was left to stand for 5 hours to remove bubbles, and coated on glass at room temperature using a coater to form a film. Then placing the film in an N2 atmosphere, and performing thermal imidization according to the procedure of 100 ℃/1h → 150 ℃/1h → 200 ℃/1h → 250 ℃/2h → 300 ℃/1h → 350 ℃/1h → 450 ℃/0.5h to obtain the polyimide film, wherein the film thickness is 10 μm.
Comparative examples 2A and 3A used s-BPPD/ODA and PMDA/ODA as the polymerization monomers, respectively, under the same conditions as above.
In comparative example 4A, the molar ratio of PPD to PMDA was 0.98: 1, other conditions were the same as in comparative example 1A.
Example 1B:
under N2 atmosphere, PPD and BPPD were mixed at a ratio of 1: a reaction was carried out at a molar ratio of 0.98 in a DMAc solvent at 50 ℃ for 5 hours to obtain a polyamic acid (PAA) solution having a solid content (mass) of 15%. 4-PEPA (molar ratio of 4-PEPA: PPD: 0.03: 1) was added to the PAA solution which was completely reacted, followed by sufficient stirring. Then, the PAA solution was left to stand for 5 hours to remove bubbles, and coated on glass at room temperature using a coater to form a film. Then put it in N2In the atmosphere, thermal imidization was carried out by a procedure of 100 ℃/1h → 150 ℃/1h → 200 ℃/1h → 250 ℃/2h → 300 ℃/1h → 350 ℃/1h → 450 ℃/0.5h to obtain a polyimide film having a film thickness of 10 μm.
In examples 1C and 1D, 4-PEPA was added in an amount of 6% and 9% (molar ratio) based on the diamine, respectively, under the same conditions as above.
In examples 2B/2C/2D and 3B/3C/3D, s-BPPD/4,4'-ODA and PMDA/4,4' -ODA are respectively selected as polymerization monomers, 4-isobutyl ethynyl phthalic anhydride is adopted as an end-capping agent to replace 4-PEPA, and the addition amounts of the end-capping agent respectively account for 3%, 6% and 9% (molar ratio) of diamine, and the other conditions are the same as those in example 1B.
In example 4B, the molar ratio of PPD to PMDA was 0.98: 1, the blocking agent used was 3-EA (molar ratio of 3-EA: PDA 0.03: 1), and the other conditions were the same as in example 1B.
Coefficient of Thermal Expansion (CTE) test
The thermal dimensional thermal stability of the polyimide film was tested in TMA tensile mode using a thermomechanical analyzer model Q400EM from TA, USA (TA instruments), in a nitrogen atmosphere at a temperature range of 40-400 ℃, a temperature rise rate of 5 ℃/min, and a static tension of 0.05N applied to a film of 10 μm thickness.
The CTE calculation method comprises the following steps:
wherein, DeltaL is the length variation when the temperature is increased to DeltaT; l is0Is the initial length of the sample.
Glass transition temperature (Tg) test
A small amount of sample was charged into a crucible and the glass transition temperature was measured in a Differential Scanning Calorimeter (DSC) type DSC Q2000. The test conditions were: in the nitrogen atmosphere, the temperature is increased from 40 ℃ to 300 ℃ for the first time at the temperature increasing rate of 10 ℃/min, then the temperature is reduced to 50 ℃, then the temperature is increased to 500 ℃ at the same temperature increasing rate, and the DSC curve in the temperature increasing process of the 2 nd test is recorded.
Thermal decomposition temperature (Td) test
About 6mg of sample to be tested was weighed and the test equipment was a DTG-60AH thermogravimetric analyzer from Shimadzu corporation, Japan. The test was carried out at 10 ℃/min to a temperature of 800 ℃ in a nitrogen atmosphere.
Table 1 thermal expansion coefficient, glass transition temperature and thermal decomposition temperature tests of examples and comparative examples.
As shown in the above table, the CTE of the polyimide exhibited a different magnitude of reduction in the examples with the addition of the end-capping agent A as compared to the comparative examples without the addition of the end-capping agent A (comparative examples 1A, 2A, 3A, 4A). In addition, Td 1% was also significantly increased. In the BPPD/PPD system, the addition of the capping agent A also increases the Tg. In addition, it can be seen from the table that the addition of 3% of capping agent a relative to the molar amount of diamine significantly improves CTE, Tg and Td. The degree of improvement in CTE, Tg and Td gradually increases with increasing addition amount of capping agent A. On the other hand, for a BPPD/PPD system, 4-PEPA, 4-isobutyl ethynyl phthalic anhydride and 3-EA can play a role in improving CTE, Tg and Td, can improve the matching degree of the polyimide material and other materials, and especially have very important significance in the field of electronic chemical materials.
In the description herein, reference to the description of the terms "one embodiment/mode," "some embodiments/modes," "example," "specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/mode or example is included in at least one embodiment/mode or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to be the same embodiment/mode or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/aspects or examples and features of the various embodiments/aspects or examples described in this specification can be combined and combined by one skilled in the art without conflicting therewith.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present application, "plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
It will be understood by those skilled in the art that the foregoing embodiments are merely for clarity of illustration of the disclosure and are not intended to limit the scope of the disclosure. Other variations or modifications may occur to those skilled in the art, based on the foregoing disclosure, and are still within the scope of the present disclosure.
Claims (10)
1. The preparation method of the polyimide material is characterized by comprising the following steps:
(1) adding a certain amount of solvent into a reactor in advance, adding a certain proportion of diamine and tetracarboxylic dianhydride into the reactor, and mechanically stirring for 1-72 h to ensure that the diamine and the tetracarboxylic dianhydride are fully subjected to polymerization reaction to generate polyamic acid;
(2) after the reaction is completed, adding an end-capping reagent A, wherein the molar ratio of the addition amount of the end-capping reagent A to the diamine is 0.001-0.2, so that the end-capping reagent A and the end group of the polyamic acid are fully reacted to obtain the polyamic acid varnish;
(3) and coating the polyamic acid varnish on a substrate to be cured into polyimide.
2. The method of claim 1, wherein the capping agent a is a phenylacetylene compound containing one carboxylic anhydride group or amino group, having a structure of formula a-C:
wherein, carboxylic acid anhydride group or amino group is directly connected with benzene ring, and group R connected with alkynyl is H, alkyl or aryl; r is preferably H, C4-C8 alkyl or C8-C14 aryl.
3. The method according to claim 2, wherein the ratio of the tetracarboxylic dianhydride: if the molar ratio of the diamine is less than 1, the end-capping agent A is a compound of formula A or formula B containing an anhydride structure; if the tetracarboxylic dianhydride: if the molar ratio of diamine is greater than 1, the blocking agent A is a compound of formula C containing an amino structure.
4. The process according to claim 1, wherein the molar weight ratio of tetracarboxylic dianhydride to diamine is from 0.7 to 1.3, preferably from 0.8 to 1.2, particularly preferably from 0.9 to 1.1.
5. The method of claim 1, wherein the diamine is selected from any combination of one or more of the following: p-phenylenediamine, m-phenylenediamine, 4' -diaminodiphenyl ether, p-methylenediphenylamine, m-methylenediphenylamine, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, bis (trifluoromethyl) benzidine, 2 ' -bis [4 (4-aminophenoxy) phenyl ] hexafluoropropane, 2 ' -bis (3-aminophenyl) hexafluoropropane, 2 ' -bis (4-aminophenyl) hexafluoropropane, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, 2 ' -bis [4- (4-aminophenoxy phenyl) ] propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4,4' -bis (3-aminophenoxy) diphenylsulfone, 9-bis (4-aminophenyl) fluorene, 9-bis (3-fluoro-4-aminophenyl) fluorene.
6. The method according to claim 1, wherein the tetracarboxylic dianhydride is selected from any combination of one or more of the following: 3,3,4, 4-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride, 3,4, 4-benzophenonetetracarboxylic dianhydride, 4,4' -oxydiphthalic dianhydride, bis (3, 4-dicarboxyphenyl) dimethylsilane dianhydride, 4, 4-bis (3, 4-dicarboxyphenoxy) diphenyl sulfide dianhydride, sulfonyl diphthalic anhydride, cyclobutanetetracarboxylic dianhydride, 4,4' - (4, 4' -isopropyldiphenoxy) bis (phthalic anhydride).
7. The production method according to claim 1, wherein the solvent is one or more solvents selected from the group consisting of an aprotic polar solvent and/or a water-soluble alcohol-based solvent; n, N-dimethylacetamide, N-methyl-2-pyrrolidone or a mixture thereof is preferred.
8. The process according to claim 1, wherein the reaction temperature is 0 to 80 ℃, preferably 20 to 50 ℃.
9. The production method according to claim 1, wherein in the step (3), the amount of the polyamic acid is 1 to 50% by mass, preferably 10 to 25% by mass, with respect to the total amount of the polyamic acid varnish.
10. The process according to claim 1, wherein the blocking agent A is added in a molar ratio of 0.01 to 0.1 based on the diamine.
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