CN106633061A - Thermal imidization method for polyimide resin - Google Patents
Thermal imidization method for polyimide resin Download PDFInfo
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- CN106633061A CN106633061A CN201611231131.6A CN201611231131A CN106633061A CN 106633061 A CN106633061 A CN 106633061A CN 201611231131 A CN201611231131 A CN 201611231131A CN 106633061 A CN106633061 A CN 106633061A
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- Prior art keywords
- polyimide resin
- hot imidization
- imidization
- polyamic acid
- hot
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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
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- 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 invention relates to a thermal imidization method for polyimide resin. The problems such as low uniformity, gray color and easiness in adhesion and agglomeration existing in solid-phase thermal imidization in the prior art are mainly solved. With the adoption of the technical scheme, the thermal imidization method for polyimide resin, disclosed by the invention, comprises the following steps: grinding a polyimide resin precursor, namely polyamide acid resin, into fine particles with the mean particle size of 10-200 microns, and controlling the residual solvent content in the polyamide acid resin to be 1-15%, and performing thermal imidization on the polyamide acid resin in dynamic vacuum thermal imidization equipment. The problems are solved, and the method can be applied to thermal imidization of the polyimide resin.
Description
Technical field
The present invention relates to a kind of hot imidization method of polyimide resin.
Background technology
Polyimides is a kind of special engineering plastics containing imide group in molecular backbone, with excellent resistance to height
The characteristics such as warm nature, mechanical property, chemical resistance, anti-wear performance, dimensional stability and insulating properties.In engineering machinery, automobile
The fields such as industry, Aero-Space and war industry have broad application prospects.
The method for preparing polyimides is generally divided into two steps, solution polycondensation synthesizing polyamides acid first, then by chemistry
Or the acid of hot imidization method synthesizing polyamides.For solvable TPI, it is impossible to as traditional polyimides passes through
Solution chemistry imidization and Precipitation acquisition polyimide resin, but in homogeneous polymer solution, need poly- by other
Compound separation engineering realizes that polyimide resin is separated with solution, and through isolated polyimide resin high temperature drying is also needed
And remove the steps such as residual solvent and obtain final polyimide.
The hot imidization of polyimides can be divided into solution hot imidization and solid phase hot imidization again.Solution hot imidization is to poly-
The dissolubility and solid content of acid amides acid precursors has special requirement, and it is de- in imidization that azeotropic dehydration reagent need to be added to remove
The micromolecular water for removing (such as CN03116356).Solid phase hot imidization is applied widely, is applicable to the imines of all polyamic acids
Change process, equipment requirement is low, and treating capacity is big.But there is lack of homogeneity, color burnt hair, easily bonding reunion in solid phase hot imidization
The problems such as.
The content of the invention
The technical problem to be solved is that solid phase hot imidization has lack of homogeneity, color in prior art
Ash, the problem that easily bonding is reunited, there is provided a kind of hot imidization method of new polyimide resin.The method has uniformity
Get well, color of resin is uniform and is difficult reunion, the advantage of coking.
To solve the above problems, the technical solution used in the present invention is as follows：A kind of hot imidization side of polyimide resin
Method, comprises the following steps：
A) polyimide resin powder is broken to into average grain diameter for 10-200 μm；
B) residual solvent content in polyamic acid resin is controlled in 1-15wt%；
C) polyamic acid resin is placed in dynamic vacuum hot imidization equipment carries out hot imidization, and hot imidization temperature is
200-300 DEG C, vacuum pressure is 0.05Pa-20KPa, polyimide resin imidization degree ＞ 80% after imidization.
In above-mentioned technical proposal, it is preferable that the crushing is adopted and includes mechanical crushing, air-flow crushing, grinding and low temperature powder
One kind in broken.
In above-mentioned technical proposal, it is preferable that described residual solvent includes DMF, N, N- dimethyl second
At least one in acid amides, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO).
In above-mentioned technical proposal, it is preferable that polyimide resin precursor polyamic acid is crushed to into average grain diameter for 20-
100μm；Residual solvent content in polyamic acid resin is controlled in 2-10wt%.
In above-mentioned technical proposal, it is preferable that the hot imidization time is 0.5～3h.
In above-mentioned technical proposal, it is preferable that hot imidization equipment includes vacuum bipyramid rotary baking oven, vacuum drum formula baking oven
And the one kind in vacuum rotating baking oven.
The present invention provides a kind of hot imidization method of polyimide resin, including by polyimide resin precursor polyamide
Acid resin is crushed to the fine grained that average grain diameter is 10-200 μm；It is 1- to control the residual solvent content in polyamic acid resin
15%.Finally, above-mentioned polyamic acid resin is placed in dynamic vacuum hot imidization equipment carries out hot imidization.Heat of the invention is sub-
Amination equipment is simple, and imidization treating capacity is big, by regulating and controlling the particle diameter and residual solvent content of polyamic acid resin and combining dynamic
State vacuum hot imidization, improves polyimide resin color, imidization uniformity and adjustability, achieves preferable technology effect
Really.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Specific embodiment
Embodiment 1
The polyamic acid polymer slurries that polymerization is obtained Precipitation, the washing of Jing methyl alcohol in methyl alcohol, is dried at 150 DEG C
Polyamic acid particle is obtained, wherein residual solvent DMA content is 1wt%, and above-mentioned polyamic acid resin is passed through
After ultra micro mechanical crushing, average grain diameter is kept to be 102 μm.The polyamic acid resin particle is placed in vacuum drum formula baking oven,
Vacuum pressure is 20KPa, and hot imidization temperature is 200 DEG C, imidization time 0.5h.Polyimide resin imidization degree is
82%.
Embodiment 2
The polyamic acid polymer slurries that polymerization is obtained Precipitation, the washing of Jing ethanol in ethanol, is dried at 100 DEG C
Polyamic acid particle is obtained, wherein residual solvent DMA content is 10wt%, above-mentioned polyamic acid resin Jing
After crossing ultra micro mechanical crushing, its average grain diameter is 102 μm.The polyamic acid resin particle is placed in vacuum drum formula baking oven,
Vacuum pressure maintains 10KPa, and hot imidization temperature is 300 DEG C, imidization time 3h.Polyimide resin imidization degree is
97%.
Embodiment 3
The polyamic acid polymer slurries that polymerization is obtained Precipitation, the washing of Jing acetone in acetone, is dried at 100 DEG C
Polyamic acid particle is obtained, wherein residual solvent DMF content is 5wt%, and above-mentioned polyamic acid resin is passed through
After high speed disintegrator is crushed, its average grain diameter is 200 μm.The polyamic acid resin particle is placed in vacuum rotating baking oven, very
Pneumatics power is 0.05Pa, and hot imidization temperature is 250 DEG C, imidization time 2h.Polyimide resin imidization degree is 95%.
Embodiment 4
The polyamic acid polymer slurries that polymerization is obtained Precipitation, the washing of Jing methyl alcohol in methyl alcohol, is dried at 50 DEG C
Polyamic acid particle is obtained, wherein residual solvent DMF content is 15wt%, above-mentioned polyamic acid resin Jing
After crossing high speed disintegrator crushing, average grain diameter is kept to be 200 μm.The polyamic acid resin particle is placed in into vacuum rotating baking oven
In, vacuum pressure is 10KPa, and hot imidization temperature is 200 DEG C, imidization time 2h.Polyimide resin imidization degree is
80%.
Embodiment 5
The polyamic acid polymer slurries that polymerization is obtained Precipitation, the washing of Jing methyl alcohol in methyl alcohol, is dried at 100 DEG C
Polyamic acid particle is obtained, wherein residual solvent 1-METHYLPYRROLIDONE content is 8wt%, and above-mentioned polyamic acid resin is through gas
After stream pulverizer is crushed, average grain diameter is kept to be 10 μm.The polyamic acid resin particle is placed in vacuum bipyramid rotary baking oven,
Vacuum pressure is 0.05Pa, and hot imidization temperature is 300 DEG C, imidization time 0.5h.Polyimide resin imidization degree is
98%.
Embodiment 6
The polyamic acid polymer slurries that polymerization is obtained Precipitation, the washing of Jing methyl alcohol in methyl alcohol, is dried at 150 DEG C
Polyamic acid particle is obtained, wherein residual solvent 1-METHYLPYRROLIDONE content is 1wt%, and above-mentioned polyamic acid resin is through gas
After stream pulverizer is crushed, average grain diameter is kept to be 10 μm.The polyamic acid resin particle is placed in vacuum bipyramid rotary baking oven,
Vacuum pressure is 20KPa, and hot imidization temperature is 250 DEG C, imidization time 1h.Polyimide resin imidization degree is
94%.
Obviously, using the method for the present invention, polyimide resin precursor polyamic acid resin is crushed to into average grain diameter is
10-200 μm of fine grained；The residual solvent content controlled in polyamic acid resin is 1-15%, then by above-mentioned polyamic acid
Resin is placed in dynamic vacuum hot imidization equipment and carries out hot imidization.Hot imidization equipment of the present invention is simple, and imidization is processed
Amount is big, by regulating and controlling the particle diameter and residual solvent content of polyamic acid resin and combining dynamic vacuum hot imidization, improves poly-
Imide resin color, imidization uniformity and adjustability, achieve preferable technique effect.
Claims (6)
1. a kind of hot imidization method of polyimide resin, comprises the following steps：
A) polyimide resin powder is broken to into average grain diameter for 10-200 μm；
B) residual solvent content in polyamic acid resin is controlled in 1-15wt%；
C) polyamic acid resin is placed in dynamic vacuum hot imidization equipment carries out hot imidization, and hot imidization temperature is 200-
300 DEG C, vacuum pressure is 0.05Pa-20KPa, polyimide resin imidization degree ＞ 80% after imidization.
2. the hot imidization method of a kind of polyimide resin according to claim 1, it is characterised in that the crushing is adopted
With including the one kind in mechanical crushing, air-flow crushing, grinding and low-temperature grinding.
3. a kind of hot imidization method of polyimide resin according to claim 1, it is characterised in that described remnants
Solvent includes at least in N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO)
Kind.
4. the hot imidization method of a kind of polyimide resin according to claim 1, it is characterised in that by polyimides
Resin precursor polyamic acid is crushed to average grain diameter for 20-100 μm；Residual solvent content in polyamic acid resin is controlled in 2-
10wt%.
5. the hot imidization method of a kind of polyimide resin according to claim 1, it is characterised in that during hot imidization
Between be 0.5～3h.
6. the hot imidization method of a kind of polyimide resin according to claim 1, it is characterised in that hot imidization sets
It is standby to include vacuum bipyramid rotary baking oven, the one kind in vacuum drum formula baking oven and vacuum rotating baking oven.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611231131.6A CN106633061A (en) | 2016-12-28 | 2016-12-28 | Thermal imidization method for polyimide resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611231131.6A CN106633061A (en) | 2016-12-28 | 2016-12-28 | Thermal imidization method for polyimide resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862539A (en) * | 2019-11-22 | 2020-03-06 | 哈尔滨工业大学 | Green preparation method of polyimide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101392056A (en) * | 2008-10-17 | 2009-03-25 | 吉林大学 | High performance and low cost polyimide preformed polymer and preparation method thereof |
| CN105111469A (en) * | 2015-09-08 | 2015-12-02 | 上海华谊（集团）公司 | Preparation method of polyamideimide fine powder |
| CN105175721A (en) * | 2015-08-17 | 2015-12-23 | 吉林大学 | Method for preparing polyimide moulding powder with uniform molecular weight distribution |
-
2016
- 2016-12-28 CN CN201611231131.6A patent/CN106633061A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101392056A (en) * | 2008-10-17 | 2009-03-25 | 吉林大学 | High performance and low cost polyimide preformed polymer and preparation method thereof |
| CN105175721A (en) * | 2015-08-17 | 2015-12-23 | 吉林大学 | Method for preparing polyimide moulding powder with uniform molecular weight distribution |
| CN105111469A (en) * | 2015-09-08 | 2015-12-02 | 上海华谊（集团）公司 | Preparation method of polyamideimide fine powder |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862539A (en) * | 2019-11-22 | 2020-03-06 | 哈尔滨工业大学 | Green preparation method of polyimide |
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Application publication date: 20170510 |