CN109337071B - Additive applied to polyimide purification and electronic grade polyimide product - Google Patents
Additive applied to polyimide purification and electronic grade polyimide product Download PDFInfo
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- CN109337071B CN109337071B CN201811105750.XA CN201811105750A CN109337071B CN 109337071 B CN109337071 B CN 109337071B CN 201811105750 A CN201811105750 A CN 201811105750A CN 109337071 B CN109337071 B CN 109337071B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 141
- 239000004642 Polyimide Substances 0.000 title claims abstract description 119
- 239000000654 additive Substances 0.000 title claims abstract description 47
- 230000000996 additive effect Effects 0.000 title claims abstract description 39
- 238000000746 purification Methods 0.000 title abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 32
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims description 37
- 238000005406 washing Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920002521 macromolecule Polymers 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
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- YTYZMZQDGZMTJM-UHFFFAOYSA-N 2-amino-1h-imidazole-5-carboxylic acid Chemical group NC1=NC=C(C(O)=O)N1 YTYZMZQDGZMTJM-UHFFFAOYSA-N 0.000 claims description 2
- QRIVRJBZKGQYKV-UHFFFAOYSA-N 5-amino-2-(4-aminophenoxy)benzenesulfonic acid Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1S(O)(=O)=O QRIVRJBZKGQYKV-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 34
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 8
- 125000003277 amino group Chemical group 0.000 abstract description 7
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- 239000003574 free electron Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 46
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 23
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 15
- 239000010408 film Substances 0.000 description 14
- 125000000524 functional group Chemical group 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000003446 ligand Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
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- 239000000178 monomer Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- -1 amino, carboxyl Chemical group 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
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- 150000004985 diamines Chemical class 0.000 description 3
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- 229910052739 hydrogen Inorganic materials 0.000 description 3
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
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- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000008065 acid anhydrides Chemical group 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZDIRKWICVFDSNX-UHFFFAOYSA-N diethyl phosphate 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium Chemical compound P(=O)(OCC)(OCC)O.C(C)N1CN(C=C1)C ZDIRKWICVFDSNX-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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 & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to the technical field of thin film materials, in particular to an additive applied to polyimide purification, an electronic grade polyimide product and a preparation method thereof. The additive has the following structural formula:
a is described1Said R is1Said R is2And said R3At least one of the groups being capable of donating a proton or having an unpaired free electron; and, said R1Said R is2And said R3The group contains at least one carboxyl or amino group. The invention selects trace additive meeting specific requirements to be complexed with impurity ions in polyamic acid or polyimide to finally form macromolecule-metal complex so as to reduce metal ions in free state and achieve the purpose of purification. The method can effectively reduce the content of metal ions in the finally obtained polyimide film and meet the use requirements of electronic-grade products.
Description
Technical Field
The invention relates to the technical field of thin film materials, in particular to an additive applied to polyimide purification, an electronic grade polyimide product and a preparation method thereof.
Background
Polyimide materials have excellent heat resistance, mechanical strength, insulation, low dielectric constant and other characteristics, and are insulation materials with relatively excellent comprehensive performance at present. Based on the above excellent characteristics, polyimide materials are widely used in electronic products, for example, they can be used for preparing a micro-component substrate insulating film, a chip carrier tape, a flexible wiring board, a liquid crystal alignment film, and the like.
The inventor discovers that in the process of implementing the invention: in the preparation and transportation process of the polyimide material, metal ion impurities are easily introduced, so that the purity of the finally prepared polyimide material is insufficient. The polyimide mixed with impurities may affect the performance of electronic devices when it is finally applied to electronic products.
Disclosure of Invention
The embodiment of the invention aims to solve the technical problem that the purity of the existing polyimide material is not enough.
In order to solve the above technical problem, one technical solution adopted by the embodiment of the present invention is: the additive applied to polyimide purification is provided, and the structural formula of the additive is as follows:
a is described1Said R is1Said R is2And said R3At least one of the groups being capable of donating a proton or having an unpaired free electron;
and, said R1Said R is2And said R3The group contains at least one carboxyl or amino group.
Optionally, the A is1Said R is1Said R is2And said R3In the group, at least one group is the following group: -OH, -COOH, -NH-, -NH2，－PH－，RO(OH)2，－SH，－C(＝S)SH。
Optionally, the A is1Said R is1The R is2And said R3In the group, at least one group is the following group: c ═ O, -COOR, -N ═ O, -NO2、－N＝N－、C＝S，－C≡N，C＝C，－SCN，－PR2。
Optionally, the A is1Is a sulfur-containing or nitrogen-containing group; the R is1The R is2And the R3All contain amino or carboxyl groups.
Optionally, the A is1And said R3Is a sulfur-containing or nitrogen-containing group; the R is1And said R2All contain amino or carboxyl groups.
Optionally, the A is1Is a sulfur-containing or nitrogen-containing group; the R is1The R is2Or said R is3One of which is an amino group or a carboxyl group, and the other two are both anionic groups.
Alternatively, the additive has the formula:
any one of the above; the R1, the R2 and the R3 are all one of hydrogen, amino, carboxyl, alkyl, a nitrogen-containing functional group and a sulfur-containing functional group.
In order to solve the above technical problems, another technical solution adopted by an embodiment of the present invention is to provide a method for preparing an electronic grade polyimide product, including: preparing a polyamic acid precursor solution or a polyimide solution; dissolving the polyamic acid precursor solution or polyimide solution in NMP or DMAc, adding the additive, heating and stirring for reaction to obtain a primarily purified polyamic ester or polyimide solution; washing and separating the primarily purified polyesteramide or polyimide solution to obtain a purified polyesteramide or polyimide solution; and preparing an electronic grade polyimide product by using the purified polyesteramide or polyimide solution.
Optionally, the NMP or DMAc is 5% to 20% wt; the weight percentage of the additive is 0.1-1 wt%.
In order to solve the above technical problem, another technical solution adopted by the embodiment of the present invention is: an electronic grade polyimide product is provided, which is obtained by the preparation method.
The invention selects trace additive meeting specific requirements to be complexed with impurity ions in polyamic acid or polyimide to finally form macromolecule-metal complex so as to reduce metal ions in free state and achieve the purpose of purification. The method can effectively reduce the content of metal ions in the finally obtained polyimide film and meet the use requirements of electronic-grade products.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing an electronic grade polyimide product according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a polyimide precursor or polyimide according to an embodiment of the present invention;
FIG. 3 is a schematic illustration of a polyimide precursor or polyimide provided by an embodiment of the present invention incorporating functionalized pendant groups;
FIG. 4 shows the results of the dielectric constant kU test of an unpurified polyimide film provided in an example of the present invention under the conditions of examples 1 to 5.
Detailed Description
In order to make the objects, aspects and advantages of the present invention more apparent, the present invention will be described in further detail with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
It is well known in the electronics industry that the performance of electronic material products at the application end determines the quality and performance of the devices. Therefore, the threshold requirements for the purity and quality of electronic materials are becoming higher and higher. According to the requirements of the international society for semiconductor industry, high-purity electronic chemicals respectively put strict requirements on several aspects such as purity, moisture, ion content, particle level, pH and the like, wherein the ion content and the particle level are bottleneck problems for restricting the high-purity chemicals, and at present, the domestic technology can reach the SEMI C-7 standard formulated by the international society for semiconductor industry at most and has a great distance from the latest SEMI Grade5 standard formulated by the international society for semiconductor industry.
As indicated in the background art, the purity of polyimide materials is very demanding when applied to the production of electronic materials. The conventional polyimide preparation and purification methods require a great cost or technical expense to meet such purity requirements. The ion adsorption column provided by the embodiment of the invention can effectively realize the purification of the polyimide material, and the high-purity electronic grade polyimide material which meets the requirements can be obtained at lower cost or technical cost.
In order to better understand the method for purifying polyimide provided by the embodiment of the present invention, the following first describes the synthesis mechanism of polyimide material in detail.
The preparation method of the polyimide film comprises the following steps: tetracarboxylic acid or dianhydride and diamine monomer react in a polar solvent at normal temperature and pressure to form polyamic acid precursor solution or polyimide solution, and the polyamic acid precursor solution or polyimide solution is subjected to film forming by a spin coating method, a tape casting method or the like. The precursor of the thin film polyamic acid precursor solution can be dehydrated and closed-loop by a thermal or chemical method to form the polyimide film.
Conventionally, materials used in the electronic industry are almost in a thin film state, and thus polyimide films are widely used.
Polyimide films have the following advantages: (1) the monomer for preparing the polyimide film is easy to obtain; (2) in the imidization and dehydration process after the polyamic acid precursor solution is thinned, the polyamic acid precursor solution can be quickly volatilized outside without generating film pores due to the film; (3) when the polyamic acid precursor solution or the polyimide solution is subjected to film formation by a spin coating method, multilayering and functionalization are easy to realize; (5) in the process of preparing the film, no curing agent, cross-linking agent and the like are required to be additionally added, and the method is suitable for the electronic industry with strict purity requirements.
Currently, in the preparation of polyimide films, tetracarboxylic acid or dianhydride is first used to react with diamine monomers. As the main functional groups of the reaction monomer are amine group and carboxyl group, certain metal ions can be brought into the amine group and the carboxyl group.
Secondly, the strong polarity of the solvents DMAc or NMP during the reaction forms very good organic electrolyte solutions with the metal ions, so that these solutions react inevitably with metal ions (Fe)3+、Al3+、Ca2+、Cu2+、Mg2+、K+Etc.).
Further, if the reaction stage is performed in a stainless steel or glass apparatus, a small amount of metal impurities must be introduced during the reaction, and if a general teflon reaction kettle is selected, the reaction kettle has poor heat transfer effect, so that the reaction temperature is not easy to control.
Meanwhile, the polytetrafluoroethylene material reaction kettle is high in investment, and due to the superposition of the factors, a large amount of metal ions are introduced and remained in the finally synthesized polyimide.
As noted above, the purity of the polyimide and the content of metal ions can affect the quality of the polyimide film, as well as the performance of the device. The high content of metal ions can lead to the increase of conductivity, so that the performance of the device is reduced, and the phenomenon of 'breakdown' is easy to occur, thereby affecting the service life of the device. Therefore, electronic grade polyimide materials are required to meet very high purity standards.
The purification method of polyimide solution used conventionally is to purify dianhydride and diamine monomers and the solvent used, and then polymerize the purified synthesis raw materials into polyamic acid or polyimide solution, so as to achieve the effects of reducing metal ions and purifying. Although such a method can reduce the effect of metal ions to some extent, it cannot avoid the problem of introducing metal ions generated in the subsequent synthesis, storage and transportation processes.
In addition, there are polyimide purification methods using precipitation, in which impurities and free metal ions are removed by washing. However, these precipitation methods are not effective because they consume a large amount of solvent and are inefficient in purification.
Compared with the conventional polyimide purification method, the embodiment of the invention starts from the synthesized polyamic acid or polyimide solution, and finally forms a macromolecular-metal complex by selecting a trace additive meeting specific requirements to be complexed with impurity ions in the polyamic acid or polyimide so as to reduce free metal ions and achieve the purpose of purification. The method can effectively reduce the content of metal ions in the finally obtained polyimide film and meet the use requirements of electronic-grade products.
Fig. 1 is a process for preparing an electronic grade polyimide product according to an embodiment of the present invention, as shown in fig. 1, the process includes the following steps:
110. a polyamic acid precursor or a polyimide solution is prepared.
The polyamic acid precursor or polyimide can be specifically prepared by adopting any conventional synthesis technology. The polyamic acid precursor or polyimide prepared in step 110 is a sample to be purified that requires metal ion purification.
120. And dissolving the polyamic acid precursor or polyimide in NMP or DMAc, adding an additive, heating, stirring and reacting to obtain a primarily purified polyamic ester or polyimide solution.
N-methylpyrrolidone (NMP) and dimethylacetamide (DMAc) are excellent solvents and can be used as a solvent for resins. Wherein, the N-methyl pyrrolidone is a polar solvent with strong selectivity and good stability. Dimethylacetamide (DMAc) is also an aprotic highly polar solvent used as a resin solvent. In this example, the NMP or DMAc is added in a weight percentage of 5% to 20% wt.
The additive is an additive capable of functionalizing the polyamic acid precursor or the polyimide. Specifically, the polyimide can be functionalized by grafting or grafting a functionalized side group on a polymer chain, wherein the weight percentage of the additive is 0.1-1 wt%. If the content of the additive is lower than the range, the additive is not beneficial to fully adsorbing metal ions in the solution, so that insufficient purification is caused; and if the content of the adsorbent is higher than the range, the cost of the additive is too high, which causes waste.
The functionalized polyimide can be used as a macromolecular ligand to interact with free metal ions in a solution to form a macromolecular-metal complex through complexation, so that the concentration of the free metal ions is effectively reduced.
130. And washing and separating the primarily purified polyesteramide or polyimide solution to obtain the purified polyesteramide or polyimide solution.
After the complexation reaction is completed, the corresponding solvent can be used for washing, and some unbound or unreacted reagents (such as additives) can be separated, so that the purification of the polyamic acid precursor or polyimide is completed.
In the subsequent production and manufacturing process, the purified polyesteramide or polyimide can be dissolved again by using a high-polarity solvent such as electronic-grade DMAc or NMP and the like to form a polyesteramide or polyimide solution which is applied to preparing a corresponding polyimide film product.
140. And preparing an electronic grade polyimide product by using the purified polyesteramide or polyimide solution.
In the purification method provided by the embodiment of the invention, the purification principle is that macromolecules such as polyamic acid precursor or polyimide are functionalized through a trace amount of additive in the polyamic acid precursor solution or polyimide solution to form a macromolecular ligand.
The generated macromolecular ligand can be complexed with free metal ions to form a macromolecular-metal ion complex, thereby achieving the effects of reducing the content of the free metal ions and purifying the polyamic acid precursor solution or the polyimide solution.
The purification method is directly carried out on the polyimide precursor or the polyimide solution after synthesis and preparation, is simple and low in cost, and can effectively improve the purification effect of the polyimide.
Based on the additive and the polyimide precursor or the polyimide purification method provided by the embodiment of the invention, the embodiment of the invention also provides a polyimide product.
The polyimide product can be prepared by adopting the purification method to prepare a polyimide precursor solution or a polyimide solution through a film coating mode and the like.
The finally purified polyimide film product can meet the requirements of electronic grade polyimide in the electronic fields of PI liquid crystal orientation films, PI film substrates, photosensitive PI and the like.
In the actual purification process, various additives can be used to functionalize the macromolecule to form the corresponding macromolecular ligand. The chemical structural formula of the additive is as follows:
the additive is prepared from A1 and R1、R2And R3Four in total. Wherein the additive should satisfy the following two conditions:
at a1、R1、R2And R3Should contain at least one protic or one aprotic group.
The protic group has an O-H bond or an N-H bond which can serve as a hydrogen bond donor and is capable of donating a proton. The protic group may be-OH, -COOH, -NH-2，－PH－，RO(OH)2-SH, -C (═ S) SH, and the like.
The aprotic group is a group or a heteroatom having an unpaired free electron capable of interacting with a free metal ion. The aprotic group may be C ═ O, -COOR, -N ═ O, -NO2，－N＝N－，C＝S，－C≡N，C＝C，－SCN，－PR2And the like.
Based on different types of additives, macromolecules in the polyimide precursor or the polyimide solution can correspondingly form proton-type or non-proton-type macromolecular ligands for carrying out a complex reaction with free metal ions to generate a stable complex.
Two, a group R in the side chain1、R2And R3Should also contain at least one amino or carboxyl group. Thus, the amino or carboxyl group located at the side chain of the additive may be bonded to the acid anhydride or amino group at the terminal of the polymer chain in the solution, thereby branching the polymer chain or adding a functional side group.
The purification process of the polyimide precursor or polyimide when different kinds of additives are added is described in detail below with reference to the reaction processes shown in fig. 2 and 3.
Fig. 2 is a schematic diagram of a polyimide precursor or polyimide branched according to an embodiment of the present invention. In this example, A of the additive1May be a sulfur-containing functional group or a nitrogen-containing functional group, R1、R2And R3Both amino and carboxyl groups.
As shown in FIG. 2, when the additive provided in this example was added, the end of the polyimide precursor or polyimide and R of the additive were compared1、R2And R3And then combined, thereby branching occurs.
Then, the branched polyimide precursor or polyimide is used as a macromolecular ligand to react with free metal ions M+Complexing, which reduces the purification effect of free metal ions.
Fig. 3 is a schematic diagram of a functional side group introduced into a polyimide precursor or polyimide according to an embodiment of the present invention. In this example, A of the additive1And R3Is a sulfur-containing functional group or a nitrogen-containing functional group, R1And R2Both amino and carboxyl groups.
As shown in FIG. 3, when the additive provided in this example was added, the end of the polyimide precursor or polyimide and R of the additive were compared1And R2Combined to introduce functional side group (R) on macromolecular chain3)。
Then, through the introduced functional side group, the polyimide precursor or polyimide is taken as a macromolecular ligand to react with free metal ions M+Complexing, which reduces the purification effect of free metal ions.
In other embodiments, when A of the additive is1When it is a sulfur-containing functional group or a nitrogen-containing functional group, R1、R2And R3Only one group in the (a) may be an amino group or a carboxyl group, and the remainder are all anionic groups.
By using the above-mentioned knotThe additive is combined with two tail ends of the head and the tail of the polyimide precursor or the polyimide respectively, so that the polyimide precursor or the polyimide forms a macromolecular ligand with functional groups at two ends of a molecular chain. Such macromolecular ligands likewise being free metal ions M+Complexing, which reduces the purification effect of free metal ions.
Specifically, according to the needs of practical situations, on the premise of satisfying the limitations disclosed in the above embodiments, the structural formula in the additive may be any one of the following:
and R in the additive1、R2And R3The moiety may be any of hydrogen, amino, carboxyl, hydrocarbyl, a nitrogen-containing functional group, or a sulfur-containing functional group.
The method for purifying the polyimide precursor or the polyimide by adding the additive provided by the embodiment of the invention is simple and efficient and has low cost. The dielectric constant of the prepared polyimide product is effectively reduced, and the requirement of the electronic product industry on the polyimide product can be met.
The invention is further illustrated below with reference to a number of specific purification and product preparation examples, but the invention is not limited to this particular example.
Example 1
1. 2.0024g (10mmol) of 4,4' -diaminodiphenyl ether and 2.2030g (10.1mmol) of pyromellitic dianhydride are weighed and dissolved in 23mL of N-methylpyrrolidone, stirred for 12H under the atmosphere of nitrogen, then 56.5mg of 1H-imidazole 2,4, 5-ethylene triamine is added, the temperature is gradually raised to 60 ℃, and then continuously stirred for 10H, thus obtaining the primarily purified polyesteramide.
2. And washing the primarily purified polyesteramide product with deionized water once, washing with methanol three times, drying, and re-dissolving with 23mL of electronic grade DMAc or NMP to obtain the purified macromolecule-metal complex.
3. The purified polyesteramide or polyimide solution was coated on a substrate to form a film, and then subjected to a dielectric constant test.
4. The dielectric constant k of the polyimide film was measured at a frequency between 10Hz and 1MHz using a Solartron SI 1260 impedance/gain phase Analyzer (Solartron Group Ltd., U.K.) at 20 ℃ and 48% relative humidity1。
Example 2
1. 2.0024g (10mmol) of 4,4' -diaminodiphenyl ether and 2.2030g (10.1mmol) of pyromellitic dianhydride are weighed and dissolved in 23mL of N-methylpyrrolidone, stirred for 12h under the atmosphere of nitrogen, then 56.5mg of 1,3, 5-triazine-2, 4, 6-triamine is added, the temperature is gradually raised to 60 ℃, and then continuously stirred for 10h, thus obtaining the primarily purified polyesteramide.
2. And washing the primarily purified polyesteramide product with deionized water once, washing with methanol three times, drying, and re-dissolving with 23mL of electronic grade DMAc or NMP to obtain the purified macromolecule-metal complex.
3. The purified polyesteramide or polyimide solution was coated on a substrate to form a film, and then subjected to a dielectric constant test.
4. The dielectric constant k of the polyimide film was measured at a frequency between 10Hz and 1MHz using a Solartron SI 1260 impedance/gain phase Analyzer (Solartron Group Ltd., U.K.) at 20 ℃ and 48% relative humidity2。
Example 3
1. 2.0024g (10mmol) of 4,4' -diaminodiphenyl ether and 2.2030g (10.1mmol) of pyromellitic dianhydride are weighed and dissolved in 23mL of N-methylpyrrolidone, stirred for 12H under the atmosphere of nitrogen, then 56.5mg of 2-amino-1H-imidazole-4-carboxylic acid is added, after the temperature is gradually raised to 60 ℃, the mixture is continuously stirred for 10H, and a primarily purified polyesteramide product is obtained.
2. And washing the primarily purified polyesteramide product with deionized water once, washing with methanol three times, drying, and re-dissolving with 23mL of electronic grade DMAc or NMP to obtain the purified macromolecule-metal complex.
3. Coating the purified polyesteramide or polyimide solution on a substrate to form a film, and then performing a dielectric constant test k3。
4. The dielectric constant of the polyimide film was measured at a frequency between 10Hz and 1MHz using a Solartron SI 1260 impedance/gain phase analyzer (Solartron Group ltd., u.k.) at 20 ℃ and 48% relative humidity.
Example 4
1. 2.0024g (10mmol) of 4,4 '-diaminodiphenyl ether and 2.2030g (10.1mmol) of pyromellitic dianhydride are weighed and dissolved in 23mL of N-methylpyrrolidone, stirred for 12h under the atmosphere of nitrogen, then 56.5mg of 4,4' -diaminodiphenyl ether-2-sulfonic acid is added, after the temperature is gradually raised to 60 ℃, the mixture is continuously stirred for 10h, and a primarily purified polyesteramide product is obtained.
2. And washing the primarily purified polyesteramide product with deionized water once, washing with methanol three times, drying, and re-dissolving with 23mL of electronic grade DMAc or NMP to obtain the purified macromolecule-metal complex.
3. The purified polyesteramide or polyimide solution was coated on a substrate to form a film, and then subjected to a dielectric constant test.
4. The dielectric constant k of the polyimide film was measured at a frequency between 10Hz and 1MHz using a Solartron SI 1260 impedance/gain phase Analyzer (Solartron Group Ltd., U.K.) at 20 ℃ and 48% relative humidity4。
Example 5
1. 2.0024g (10mmol) of 4,4' -diaminodiphenyl ether and 2.2030g (10.1mmol) of pyromellitic dianhydride are weighed and dissolved in 23mL of N-methylpyrrolidone, stirred for 12h under the atmosphere of nitrogen, then 56.5mg of 1-ethyl-3-methylimidazole diethylphosphoric acid is added, and after the temperature is gradually raised to 60 ℃, the mixture is continuously stirred for 10h, thus obtaining the primarily purified polyesteramide product.
2. And washing the primarily purified polyesteramide product with deionized water once, washing with methanol three times, drying, and re-dissolving with 23mL of electronic grade DMAc or NMP to obtain the purified macromolecule-metal complex.
3. The purified polyesteramide or polyimide solution was coated on a substrate to form a film, and then subjected to a dielectric constant test.
4. The dielectric constant k of the polyimide film was measured at a frequency between 10Hz and 1MHz using a Solartron SI 1260 impedance/gain phase Analyzer (Solartron Group Ltd., U.K.) at 20 ℃ and 48% relative humidity5。
Example 6
The unpurified polyimide film was subjected to the same dielectric constant k under the conditions of examples 1 to 5UAnd testing, wherein the test result is shown in figure 4.
From the above test results, it can be observed that the polyimide films purified in examples 1 to 5 exhibited low dielectric constants, k respectively1＝3.218(10KHz)，k2＝3.191(10KHz)，k3＝3.176(10KHz)，k4＝3.156(10KHz)，k53.155(10KHz), while the dielectric constant of the unpurified polyimide film is kUThe dielectric constant is significantly reduced at 3.36.
The above experimental results show that, after the additive defined by the invention is added, polyamic acid, polyimide and metal ions form a macromolecule-metal complex, the free metal ions are reduced, the polyimide is thin and purified, and the dielectric constant is obviously reduced.
On the other hand, the unpurified polyimide film shows a tendency of lowering of dielectric constant in a low frequency region (< 100Hz) due to polarization of ions at the interface. It is also demonstrated that the trace additives added in examples 1-5 form a macromolecular-metal complex, so that free gold ions are reduced, the dielectric constant is reduced, and the industrial requirements are met.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (3)
1. A method of preparing an electronic grade polyimide product, the method comprising:
preparing a polyamic acid precursor solution or a polyimide solution;
dissolving the polyamic acid precursor solution or the polyimide solution in NMP or DMAc, adding an additive, heating and stirring for reaction to obtain preliminarily purified polyamic acid or polyimide solution, wherein the weight percentage of the additive is 0.1-1 wt%, and the additive is used for grafting or grafting a functional side group on a macromolecule chain of the polyamic acid precursor or the polyimide;
washing and separating the primarily purified polyamic acid or polyimide solution to obtain a purified polyamic acid or polyimide solution;
and preparing an electronic grade polyimide product by using the purified polyamic acid or polyimide solution, wherein the additive is 2-amino-1H-imidazole-4-carboxylic acid or 4,4' -diaminodiphenyl ether-2-sulfonic acid.
2. The method of claim 1, wherein said NMP or DMAc is present in an amount of 5 to 20 wt%.
3. An electronic grade polyimide product obtained by the production method according to any one of claims 1 to 2.
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