CN1174026C - Method for preparing polyimide molding powder - Google Patents
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- CN1174026C CN1174026C CNB011389079A CN01138907A CN1174026C CN 1174026 C CN1174026 C CN 1174026C CN B011389079 A CNB011389079 A CN B011389079A CN 01138907 A CN01138907 A CN 01138907A CN 1174026 C CN1174026 C CN 1174026C
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Abstract
The present invention relates to a method for preparing high performance polyimide moulding powder. A chemical imidation method and a thermal imidation method are combined by the present invention to prepare polyimide moulding powder, and more specifically, at least one kind of aromatic acid anhydride and at least one kind of aromatic diamine are polymerized in a solvent to generate a polyamide acid solution. After the chemical imidation of the polyamide acid solution is carried out at a temperature of 5 to 40 DEG C, the polyamide acid solution is heated to 50 DEG C to 250 DEG C to carry out thermal imidation reaction, and the polyimide moulding powder is obtained. The polyimide moulding powder prepared by the method has the advantages of stable quality and excellent performance.
Description
Technical field:
The invention relates to a kind of method for preparing polyimide molding powder.Specifically, be the method for preparing high-performance polyimide molding powder about a kind of, this molding powder can be used for the polyimide molding material of processing machinery excellent property.
Background technology:
The polyimide molding material is the macromolecular material that a class has significant application value, is widely used in fields such as Aeronautics and Astronautics, electric, mechanical, chemical industry, microelectronics.Such material not only has the favorable mechanical performance, and has good thermotolerance, chemicals-resistant corrodibility and insulating property.
The polyimide molding material is that polyimide molding powder is placed mould, and compression moulding obtains under High Temperature High Pressure, and the quality of polyimide molding powder directly affects performance index such as the thermostability, shock resistance, physical strength of prepared material.The quality of polyimide molding powder depends on the factors such as kind, the ratio between each monomer and synthetic method of polymerization single polymerization monomer.Usually, for the polyimide molding powder of given monomeric species, its physics is relevant with molecular weight distribution with the molecular weight size with chemical property; And ratio between polymerization single polymerization monomer and synthetic method are very big to molecular weight size and molecular weight distribution influence.Therefore, in order to obtain the polyimide molding powder of excellent property, need to select the stoichiometric ratio of suitable synthetic method and strict control reactant.
The preparation polyimide molding powder can adopt melt-polycondensation or solution polycondensation.The polymerization temperature height of melt-polycondensation is usually more than 250 ℃.Because different polymerization single polymerization monomers have different volatility, therefore adopt melt-polycondensation to be difficult to the accurately actual effective level ratio of control reactant.In addition, in melt phase polycondensation, reaction mixture viscosity is very big, is difficult for further processing.
The solution polycondensation synthesis of polyimides can be controlled the ratio of polymerization single polymerization monomer in the reaction process.Solution polycondensation is first by the acid of polymerization single polymerization monomer synthesizing polyamides, then the polyamic acid cyclodehydration is made the process of polyimide.According to the difference of polyamic acid imidization mode, solution polycondensation can be divided into chemical imidization method and hot-imide method.
Chemistry imidization method is to adopt chemical dehydrator to make polyamic acid generation cyclodehydration and the process of carrying out imidization.The chemistry imidization at room temperature carries out usually.Patent US5,189,115 reported method are to add dewatering agent acetic anhydride and catalyzer pyridine in polyamic acid solution, at room temperature react 15 hours with on prepare polyimide.The chemical cyclisation of polyamic acid also may generate different imide except that forming imide ring.Because poly-different imide is soluble in N than corresponding polyimide, in the non-proton dipole solvents such as N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, therefore different imide is difficult to be converted into fully imide under the low temperature, imidization thoroughly can not cause molecular weight of product to distribute broadening, the performance of polyimide is had a negative impact.
The hot-imide method is that polyamic acid solution is heated to more than the vaporization temperature, refluxes to remove and anhydrates, thereby the process of imidization takes place.English Patent BP1,283,077 and Japanese Patent JP4,142,332 respectively with pyromellitic acid dianhydride (PMDA) and 4, and (4,4 '-ODA) is polymerization single polymerization monomer to 4 '-diaminodiphenyl oxide, adopts the hot-imide method to synthesize the high-molecular weight polyimide.But this method is not suitable for the imidization process of the polyamic acid of less stable, because polyamic acid can be converted into low-molecular-weight polyimide under the low temperature, then can cause the decomposition of polyamic acid during high temperature; In the imidization process, along with the rising of temperature, the polyimide molecule amount skewness that is generated, thus can influence the performance of the finished product.
Summary of the invention:
The preparation method who the purpose of this invention is to provide the polyimide molding powder of a kind of stable performance and good quality of product.This method both can have been avoided the unmanageable problem of the ratio of reactant in the melt-polycondensation, can avoid the problem of the polyimide molecule amount wider distribution of traditional solution polycondensation preparation again.Adopt method of the present invention to prepare polyimide molding powder, can effectively control the quality of the composition and the product of product.
According to the present invention, the preparation method of polyimide molding powder combines chemical imidization method with the hot-imide method, at first polyamic acid solution is carried out chemical imidization under 5～40 ℃, has avoided the degraded of polyamic acid under the high temperature; Carry out hot-imide at 50～250 ℃ then,, make it to change into fully polyimide to guarantee the thorough imidization of polyamic acid.
According to the present invention, the chemical imidization of synthetic polyamic acid solution is to carry out in the presence of the dewatering agent of routine and catalyzer, and the polyimide of generation is separated out from solution with powder type.Temperature of reaction in the chemistry imidization process is 5～40 ℃, and preferable temperature of reaction is 10～35 ℃; Reaction times is 1.0h～25.0h, and the preferable reaction times is 2.0h～20.0h.Used dewatering agent can be in diacetyl oxide, Glacial acetic acid, sulfur oxychloride, trifluoroacetic anhydride, benzoyl oxide, propionic anhydride, the butyryl oxide one or more; Used catalyzer can be in pyridine, aliphatics amine, pyridone class, aminopyridines or the tosic acid one or more.
According to the present invention, polyamic acid needs further to carry out conventional hot-imide process behind chemical imidization, and the solution that is about to contain polyimide powder is heated to assigned temperature and carries out hot imide reaction.Temperature of reaction is 50 ℃～250 ℃, and preferable temperature of reaction is 80 ℃～200 ℃; Reaction times is 1.0h～15.0h, and the preferable reaction times is 2.0h～10.0h.Further the polyimide powder 160 ℃ of dry 10h in vacuum drying oven that obtain behind the hot-imide promptly obtain the polyimide molding powder product.
According to the present invention, synthesizing polyamides acid solution at first, being about to the polymerization in solvent of at least a aromatic anhydride and at least a aromatic diamine, to generate solid content be 10%～30% polyamic acid solution.Temperature of reaction is 0～35 ℃; Reaction times is 0.5h～25.0h, and the preferable reaction times is 2.0h～15.0h.
The structural formula of wherein a kind of polyamic acid provided by the invention is represented suc as formula (1):
Wherein, R
0For having the tetravalence aromatic base of 6～30 C atoms, R
1For having the divalence aromatic base of 6～30 C atoms, n is 50～1000 integer.
The used aromatic anhydride of synthesizing polyamides acid can be in the following compound one or more:
Used aromatic diamine can be in the following compound one or more:
The mol ratio of aromatic anhydride and aromatic diamine is 0.8: 1.0～1.2: 1.0, and preferable mol ratio is 0.9: 1.0～1.1: 1.0.When the two mol ratio is 1.0: 1.0, need to use chain terminator; Chain terminator can be an aniline, also can be Tetra hydro Phthalic anhydride, and the consumption of chain terminator is 0.005～5.0% (mass percent) of total reactant consumption, and preferable consumption is 0.1～2.0% (mass percent).
The used solvent of synthesizing polyamides acid can be N,N-dimethylacetamide (DMAc), N-Methyl pyrrolidone (NMP), N, one or more in dinethylformamide (DMF), the dimethyl sulfoxide (DMSO) non-proton dipole solvents such as (DMSO).
The structural formula of the final polyimide molding powder product of this polyamic acid is as follows:
Wherein, R
0For having the tetravalence aromatic base of 6～30 C atoms, R
1For having the divalence aromatic base of 6～30 C atoms, n is 50～1000 integer.
The method that the present invention prepares polyimide molding powder has simple to operate, the wield characteristic of processing condition, by the polyimide molding powder steady quality and the excellent property of the present invention's preparation.
Embodiment:
Embodiment 1
In the 1000ml round-bottomed flask, with 32.72 gram pyromellitic acid dianhydrides, 30.04 grams 4,4 '-diaminodiphenyl oxide and 0.63 gram aniline are dissolved in the 464.86 gram N,N-dimethylacetamide, stirred 4 hours down at 20 ℃, obtain solid content and be 12% polyamic acid solution.
In polyamic acid solution, add 52.83 gram Glacial acetic acid and 11.6 gram pyridines, 30 ℃ stir 3 hours down after, separate out polyimide powder in the solution, with this mixed solution that contains polyimide powder 120 ℃ of heated and stirred 4 hours.With the mixed solution cooled and filtered, the powder that obtains 160 ℃ of dryings 10 hours in vacuum drying oven obtain the polyimide molding powder product.The second-order transition temperature of this product is 418 ℃.
Embodiment 2
In the 1000ml round-bottomed flask, with 48.34 gram benzophenone tetracarboxylic dianhydrides, 30.04 grams 4,4 '-diaminodiphenyl oxide and 0.39 gram aniline are dissolved in the 446.36 gram N,N-dimethylacetamide, stirred 6 hours down at 25 ℃, obtain solid content and be 15% polyamic acid solution.
In polyamic acid solution, add 52.51 gram acetic anhydrides and 8.67 gram triethylamines, 30 ℃ stir 5 hours down after, separate out polyimide powder in the solution, with this mixed solution that contains polyimide powder 140 ℃ of heated and stirred 6 hours.With the mixed solution cooled and filtered, the powder that obtains 160 ℃ of dryings 10 hours in vacuum drying oven obtain the polyimide molding powder product.The second-order transition temperature of this product is 283 ℃.
Embodiment 3
In the 1000ml round-bottomed flask, 48.86 gram phenyl ether tetracarboxylic dianhydrides, 16.22 gram Ursol D are dissolved in the 479.67 gram N-Methyl pyrrolidone with 0.33 gram Tetra hydro Phthalic anhydride, 25 ℃ of stirrings 5 hours down, obtain solid content and be 12% polyamic acid solution.
In polyamic acid solution, add 54.51 gram propionic anhydrides and 8.53 gram 4-Dimethylamino pyridines, 30 ℃ stir 4 hours down after, separate out polyimide powder in the solution, with this mixed solution that contains polyimide powder 170 ℃ of heated and stirred 5 hours.With the mixed solution cooled and filtered, the powder that obtains 160 ℃ of dryings 10 hours in vacuum drying oven obtain the polyimide molding powder product.The second-order transition temperature of this product is 335 ℃.
Embodiment 4
In the 500ml round-bottomed flask, with 31.02 gram phenyl ether tetracarboxylic dianhydrides, 19.02 grams 4,4 '-diaminodiphenyl oxide and 1.02 gram aniline are dissolved in the 204.24 gram N,N-dimethylacetamide, stirred 5 hours down at 20 ℃, obtain solid content and be 20% polyamic acid solution.
In polyamic acid solution, add 25.53 gram Glacial acetic acid and 6.74 gram 2 hydroxy pyrimidines, 35 ℃ stir 6 hours down after, separate out polyimide powder in the solution, with this mixed solution that contains polyimide powder 120 ℃ of heated and stirred 4 hours.With the mixed solution cooled and filtered, the powder that obtains 160 ℃ of dryings 10 hours in vacuum drying oven obtain the polyimide molding powder product.The second-order transition temperature of this product is 264 ℃.
Embodiment 5
In the 1000ml round-bottomed flask, with 37.23 gram phenyl ether tetracarboxylic dianhydrides, 30.66 grams 4,4 '-diaminodiphenylsulfone(DDS) and 0.69 gram Tetra hydro Phthalic anhydride are dissolved in the 388.62 gram N-Methyl pyrrolidone, stir 4 hours down at 20 ℃, obtain solid content and be 15% polyamic acid solution.
In polyamic acid solution, add 45.72 gram acetic anhydrides and 5.90 gram pyridines, 35 ℃ stir 6 hours down after, separate out polyimide powder in the solution, with this mixed solution that contains polyimide powder 140 ℃ of heated and stirred 4 hours.With the mixed solution cooled and filtered, the powder that obtains 160 ℃ of dryings 10 hours in vacuum drying oven obtain the polyimide molding powder product.The second-order transition temperature of this product is 315 ℃.
Claims (8)
1. a method for preparing polyimide molding powder is characterized in that, with polyamic acid, under 5～40 ℃, dewatering agent and catalyzer existence condition, carries out chemical imidization; Under 50 ℃～250 ℃ conditions, prepare polyimide molding powder again through hot-imide.
2. according to the described method for preparing polyimide molding powder of claim 1, it is characterized in that the used dewatering agent of chemical imidization is one or more in diacetyl oxide, Glacial acetic acid, sulfur oxychloride, trifluoroacetic anhydride, benzoyl oxide, propionic anhydride, the butyryl oxide; Used catalyzer is one or more in pyridine, aliphatics amine, pyridone class, aminopyridines or the tosic acid.
3. according to the described method for preparing polyimide molding powder of claim 1, it is characterized in that the hot imide reaction temperature is 80 ℃～200 ℃.
4. according to the described method for preparing polyimide molding powder of claim 1, it is characterized in that, polymerization generation solid content in solvent is 10%～30% polyamic acid solution with at least a aromatic anhydride and at least a aromatic diamine, and temperature of reaction is 0～35 ℃; Reaction times is 0.5h～25.0h.
5. according to the described method for preparing polyimide molding powder of claim 4, it is characterized in that, when described polyamic acid, when its structural formula is represented suc as formula (1):
Wherein, R
0For having the tetravalence aromatic base of 6～30 C atoms, R
1For having the divalence aromatic base of 6～30 C atoms, n is 50～1000 integer;
The used aromatic anhydride of synthesizing polyamides acid is one or more in the following compound:
(wherein X=O, SO
2, CO, C (CF
3)
2)
Used aromatic diamine is one or more in the following compound:
The mol ratio of aromatic anhydride and aromatic diamine is 0.8: 1.0～1.2: 1.0;
The used solvent of synthesizing polyamides acid is N,N-dimethylacetamide (DMAc), N-Methyl pyrrolidone (NMP), N, one or more in dinethylformamide (DMF), the dimethyl sulfoxide (DMSO) non-proton dipole solvents such as (DMSO).
6. according to the described method for preparing polyimide molding powder of claim 5, it is characterized in that the mol ratio of aromatic anhydride and aromatic diamine is 0.9: 1.0～1.1: 1.0.
7. according to the described method for preparing polyimide molding powder of claim 6, it is characterized in that, the mol ratio of aromatic anhydride and aromatic diamine is 1.0: 1.0 o'clock, need to use chain terminator, chain terminator is an aniline, or Tetra hydro Phthalic anhydride, the consumption of chain terminator is 0.005～5.0% mass percent of total reactant consumption.
8. according to the described method for preparing polyimide molding powder of claim 6, it is characterized in that the consumption of chain terminator is 0.1～2.0% mass percent of total reactant consumption.
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| CNB011389079A CN1174026C (en) | 2001-12-25 | 2001-12-25 | Method for preparing polyimide molding powder |
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| CNB011389079A CN1174026C (en) | 2001-12-25 | 2001-12-25 | Method for preparing polyimide molding powder |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100511B (en) * | 2006-07-05 | 2011-06-29 | 达兴材料股份有限公司 | Polyimide resin polymer and liquid crystal alignment layer material containing the same |
| CN117069939A (en) * | 2023-10-17 | 2023-11-17 | 宁德时代新能源科技股份有限公司 | Polyimide microsphere and preparation method thereof, negative electrode plate, battery and power utilization device |
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| DE102005034969A1 (en) * | 2005-07-22 | 2007-02-08 | Inspec Fibres Gmbh | Process for the preparation of a block copolymer of polyimides and use of the block copolymer for the production of powders and moldings |
| CN100412111C (en) * | 2006-09-05 | 2008-08-20 | 东华大学 | Preparation method of phenolic hydroxyl group containing polyimide powder |
| CN100441652C (en) * | 2007-01-19 | 2008-12-10 | 东华大学 | Method for preparing binder of polyimide of containing phenolic hydroxyl group |
| CN101412812B (en) * | 2008-10-28 | 2011-07-20 | 上海三普化工有限公司 | Method for aqueous phase synthesis of polyimides |
| CN102108124A (en) * | 2010-12-30 | 2011-06-29 | 上海市合成树脂研究所 | Preparation method of meltable polyimide moulding compound |
| CN113321806A (en) * | 2020-02-29 | 2021-08-31 | 上海市合成树脂研究所有限公司 | Heat-conducting polyimide composite molding plastic and manufacturing method thereof |
| CN113736350B (en) * | 2021-09-15 | 2022-05-17 | 安徽华辉塑业科技股份有限公司 | High-brightness coating and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100511B (en) * | 2006-07-05 | 2011-06-29 | 达兴材料股份有限公司 | Polyimide resin polymer and liquid crystal alignment layer material containing the same |
| CN117069939A (en) * | 2023-10-17 | 2023-11-17 | 宁德时代新能源科技股份有限公司 | Polyimide microsphere and preparation method thereof, negative electrode plate, battery and power utilization device |
| CN117069939B (en) * | 2023-10-17 | 2024-04-09 | 宁德时代新能源科技股份有限公司 | Polyimide microsphere and preparation method thereof, negative electrode plate, battery and power utilization device |
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