CN110156992A - A kind of preparation and its application of aqueous polyimides - Google Patents
A kind of preparation and its application of aqueous polyimides Download PDFInfo
- Publication number
- CN110156992A CN110156992A CN201910504684.1A CN201910504684A CN110156992A CN 110156992 A CN110156992 A CN 110156992A CN 201910504684 A CN201910504684 A CN 201910504684A CN 110156992 A CN110156992 A CN 110156992A
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- polyimides
- aqueous
- aqueous polyimides
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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
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention provides a kind of aqueous polyimides and its methods for making and using sames, by being prepared according to the following component of mass fraction meter: diacid 20-80 parts by weight, diamines 25-85 parts by weight, neutralizer 5-15 parts by weight, solvent 10-100 parts by weight, flame-retardant conductive glue of the present invention have preferable bonding fastness, heat resistance and excellent electric conductivity, have preferable use value, and organic solvent is free of, meet the environmentally protective theory of today's society.
Description
Technical field
The present invention relates to polyimides synthesis technical fields, and in particular to a kind of aqueous polyimides.It is prepared by the present invention
Aqueous polyimides, solve that traditional polyimides dissolubility is poor, processing temperature is high, thus its application is subject to certain restrictions
Problem, and solve in solvent type polyimides preparation process and must be polluted the environment with a large amount of organic solvents, and no-solvent type PI
Working condition is again excessively harsh, and the higher problem of production cost can be widely applied to every field.
Background technique
Polyimides (PI) is a kind of high performance polymer material containing imide ring, have excellent thermal stability,
Mechanical performance and electrical property are widely used in the high-tech areas such as aerospace, automobile, microelectronics.But since traditional gathers
Acid imide dissolubility is poor, processing temperature is high, thus its application receives certain restrictions, and in solvent type polyimides preparation process
It must be polluted the environment with a large amount of organic solvents, and no-solvent type PI working condition is excessively harsh, production cost is higher.Therefore,
Synthesis and exploitation to aqueous polyimides just become the important topic for developing PI.
Summary of the invention
Goal of the invention: for the prior art defect, the purpose of the present invention is to solve traditional polyimides is molten
The problem of solution property is poor, processing temperature is high, thus its application is subject to certain restrictions, and solve solvent type polyimides preparation process
In must be polluted the environment with a large amount of organic solvents, and no-solvent type PI working condition is excessively harsh, and production cost is higher to ask
Topic.
Technical solution: to achieve the above object, the present invention is achieved through the following technical solutions: diacid 20-80 parts by weight, and two
Amine 25-85 parts by weight, neutralizer 5-15 parts by weight, solvent 10-100 parts by weight.
The preparation method of above-mentioned aqueous polyimides, comprising the following steps:
It is heated under stiring with diamines and dianhydride, when temperature reaches 100 DEG C or so, starts that water, simultaneous reactions system is precipitated
Gradually become auburn homogeneous solution.Continue to heat, reaction system temperature gradually rises, and viscosity also increases simultaneously.About through one
Temperature reaches 130 DEG C after hour, and water continues to be precipitated, until it is reaction end that reactant residual acid value ratio, which is 22%,.It is cooled to 80-
Neutralizer is added at 110 DEG C, just forms the ammonium salt of polyamic acid.After ammonium salt to be formed, remaining ammonia is steamed, can be obtained several
The not aqueous polyimides of ammonia taste.
| Performance | Numerical value | Unit |
| Stretch modulus | 4.0 | GPa |
| Thermal expansion coefficient | 1×10-6 | /℃ |
| Dielectric strength | 200 | Kv/mm |
Aqueous polyimides of the present invention has excellent thermal stability, mechanical performance and electrical property, can be extensive
Applied in the high-tech areas such as aerospace, automobile, microelectronics.
Specific implementation method
The following describes the present invention further through the description of specific embodiments, but it is to limit of the invention that this, which is not,
System, those skilled in the art's basic thought according to the present invention can make various modifications or improvements, but without departing from this
The basic thought of invention, is all within the scope of the present invention.
Case study on implementation one:
Heated under stiring with ODA and PMDA, when temperature reaches 100 DEG C or so, start to be precipitated water, simultaneous reactions system by
Fade to auburn homogeneous solution.Continue to heat, reaction system temperature gradually rises, and viscosity also increases simultaneously.It is about small through one
When after temperature reach 130 DEG C, water continues to be precipitated, until reactant residual acid value ratio be 22% be reaction end.It is cooled to 80-
Ammonia spirit is added at 110 DEG C, just forms the ammonium salt of polyamic acid.After ammonium salt to be formed, remaining ammonia is steamed, can be obtained
Almost without the aqueous polyimides of ammonia taste
| Performance | Numerical value | Unit |
| Stretch modulus | 4.0 | GPa |
| Thermal expansion coefficient | 1×10-6 | /℃ |
| Dielectric strength | 200 | Kv/mm |
Case study on implementation two:
1 molar double-core trimellitic acid dianhydride and 1 gram molecule 4,4 '-diaminodiphenylmethane are in 400 grams of ethylene glycol
In heat 45 minutes at 120 DEG C, 100 grams of diethanol amine, 280 grams of water are then added, obtain polymer solution after stirring.This is molten
Liquid, which is applied on copper wire, can obtain the polyimide insulative coating with excellent flexible performance after baking.
| Performance | Numerical value | Unit |
| Stretch modulus | 4.0 | GPa |
| Thermal expansion coefficient | 1×10-6 | /℃ |
| Dielectric strength | 200 | Kv/mm |
Case study on implementation three:
Pyromellitic acid anhydride (PMDA, 22.6g, 0.10mol) is passed through in degassing distilled water (250cm3) in reflux it is 1 small
When, complete hydrolysis is tetrabasic carboxylic acid.4,4 '-diaminodiphenyl ethers (4,4 '-ODA, 21.13g, 0.105mol) are added in solution,
It is vigorously stirred under reflux temperature more than five minutes, is then cooled to room temperature while stirring.A kind of thin white solid is analysed from solution
Out, after the evacuation and flushing into excessively several circulations, the nitrogen that positive pressure is about 20psi is filled in container.The mixture of synthesis
It is quantitatively transferred to the glass lining of Paar pressure vessel.Reaction mixture is heated to 135 DEG C, and stirs 1 hour.Temperature liter
Height is kept for 2 hours to 180 DEG C, is cooled to room temperature while stirring later.The solid of pale orange is removed from reaction vessel
Come, by filtering and being rinsed with water and then grind into powder.Continue to use hot water (100cm3), methanol (100cm3), acetone
(100cm3), methylene chloride (100cm is finally used in cleaning3) cleaning.Product is dried overnight simultaneously in about 50 DEG C of vacuum drying oven
It is collected into light orange powder (35.0g, 87.5%).
| Performance | Numerical value | Unit |
| Stretch modulus | 4.0 | GPa |
| Thermal expansion coefficient | 1×10-6 | /℃ |
| Dielectric strength | 200 | Kv/mm |
Claims (7)
1. a kind of aqueous polyimides, which is characterized in that its raw material components includes:
Diacid 20-80 parts by weight, diamines 25-85 parts by weight, neutralizer 5-15 parts by weight, solvent 10-100 parts by weight.
2. a kind of aqueous polyimides as described in claim 1, which is characterized in that its raw material components includes:
Diacid 30-70 parts by weight, diamines 35-75 parts by weight, organic amine neuutralizer 6-13 parts by weight, solvent 15-90 parts by weight.
3. a kind of aqueous polyimides as described in claim 1, which is characterized in that prepare the reaction formula of aqueous polyimides
Are as follows:
。
4. a kind of aqueous polyimides as described in claim 1, which is characterized in that the diamines is ODA, MPD, BAPP,
HDA, DDS, m-phenylene diamine (MPD), o-phenylenediamine, one or more of mixing, and be not limited to these types of diamines.
5. a kind of aqueous polyimides as described in claim 1, which is characterized in that the dianhydride is PMDA, BPDA, BTDA,
One or more of ODPA, TDPA, HQDPA mixing, and it is not limited to these types of dianhydride.
6. a kind of aqueous polyimides as described in claim 1, which is characterized in that the neutralizer is triethanolamine, diethyl
The mixing of one or more of hydramine, ethylenediamine, triethylamine, diethylamine, ethanol amine, ammonium hydroxide, dimethylethanolamine, pyridine,
And it is not limited to these types of neutralizer.
7. a kind of aqueous polyimides as described in claim 1, which is characterized in that the solvent be water, ethyl alcohol, ethylene glycol,
DMF, DMAc, acetone, the mixing of NMP, DMSO one or more, and it is not limited to these types of solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910504684.1A CN110156992A (en) | 2019-06-10 | 2019-06-10 | A kind of preparation and its application of aqueous polyimides |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910504684.1A CN110156992A (en) | 2019-06-10 | 2019-06-10 | A kind of preparation and its application of aqueous polyimides |
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| Publication Number | Publication Date |
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| CN110156992A true CN110156992A (en) | 2019-08-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201910504684.1A Withdrawn CN110156992A (en) | 2019-06-10 | 2019-06-10 | A kind of preparation and its application of aqueous polyimides |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591547A (en) * | 2019-09-21 | 2019-12-20 | 盐城增材科技有限公司 | Flame-retardant heat-insulation water-based polyimide coating and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1590464A (en) * | 1976-11-10 | 1981-06-03 | Basf Ag | Aqueous polyimide dispersions |
| CN101139501A (en) * | 2007-10-11 | 2008-03-12 | 同济大学 | Polyimide thermostable aqueous dispersion coating material and preparation method and use thereof |
-
2019
- 2019-06-10 CN CN201910504684.1A patent/CN110156992A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1590464A (en) * | 1976-11-10 | 1981-06-03 | Basf Ag | Aqueous polyimide dispersions |
| CN101139501A (en) * | 2007-10-11 | 2008-03-12 | 同济大学 | Polyimide thermostable aqueous dispersion coating material and preparation method and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| 严昌虹: ""由水溶性聚酰胺酸制备聚酰亚胺"", 《绝缘材料通讯》, pages 34 - 41 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591547A (en) * | 2019-09-21 | 2019-12-20 | 盐城增材科技有限公司 | Flame-retardant heat-insulation water-based polyimide coating and application thereof |
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Application publication date: 20190823 |
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