CN1186368C - Method for preparing molding powder of polyimide - Google Patents
Method for preparing molding powder of polyimide Download PDFInfo
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- CN1186368C CN1186368C CN 03116356 CN03116356A CN1186368C CN 1186368 C CN1186368 C CN 1186368C CN 03116356 CN03116356 CN 03116356 CN 03116356 A CN03116356 A CN 03116356A CN 1186368 C CN1186368 C CN 1186368C
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- polyimide
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Abstract
The present invention relates to a process for preparing polyimide acid by the reaction of aromatic di-amine and di-anhydride. in the beginning, a mixed solvent composed of one of non-protonic polar solvents (such as dimethyl formamide, dimethyl acetamide or N-methylpyrrolidone) and toluene or xylene is added; meantime, the same or different polyimide fine powder whose intrinsic viscosity is from 0.5 to 1.5 dL/g is added. The polyimide acid is made into polyimide moulding powder by thermal dehydration. The powder has the intrinsic viscosity eta int=1.0 to 1.5 dL/g; the bulk density is from 400 to 500 g/L. The mechanical performance of molded parts prepared by hot-pressing and sintering is 7.7% of destructive elongation rate; the non-notch impact strength is 308 J/m; the elastic modulus is 4.5GPa.
Description
(1) technical field
The present invention relates to the preparation method and the application thereof of polyimide molding powder.
(2) background technology
The polyimide molding material in the application in the industry of aerospace industry and nuclear power and other high temperature resistant field more and more widely, for example as aircraft jet engine part and tagblock and deceleration transmission gear; Mechanical component axle sleeve and bearing and seal washer; Printer elements and junctor.The polyimide molding product from now on will be with annual 8% speed increase according to estimates.Because polyimide molding material excellent performance, its many Application Areass are that other materials is irreplaceable.For this reason, just a lot of to its preparation research of raw material polyimide molding powder, prior art U.S.Pat.NO.4,413,117 is exactly an example.This method is to add the water azeotropic solvent in the aromatic polyamic acid solution of limiting viscosity 1.5 ∽ 2.5dL/g, with the mixture heating up that forms, boiling point to azeotropic solvent, make polyamic acid be converted into polyimide, simultaneously the water that is generated and azeotropic solvent azeotropic are together steamed, follow the polyimide powder that is settled out in the filtering solution, and with this powder drying, acquired character viscosity is the polyimide powder of 0.6 ∽ 1.2dL/g, loose density 200 ∽ 300g/L as a result.With this powder in 360 ℃ under 625Mpa pressure High Temperature High Pressure sinter moulded piece into, its mechanical property is as follows:
Elongation at failure 2.6%
Notched Izod impact strength 2.64KJ/m
2
Hardness H3O=294MPa
Young's modulus 4.9GPa
The advantage of prior art is entrainer and the water azeotropic steams after simple separation is reusable; Can make high-molecular weight polyimide powder (limiting viscosity is 0.6 ∽ 1.2dL/g); The satisfactory mechanical property of plastic part.Weak point is that loose density is 200 ∽ 300g/L, and in light weight, volume is big, and High Temperature High Pressure is fired the moulded piece troublesome poeration.For this reason, present inventors want to solve this shortcoming, have proposed content of the present invention.
(3) summary of the invention
The present invention is in order to improve the processing characteristics of prior art products, and contriver's new solution is perfect through experimental study, has proposed the ideal preparation method.The aromatic diamine of mol ratios such as employing of the present invention and aromatic series dianhydride, in 50 ℃ of room temperature ∽ at aprotic polar solvent as dimethyl formamide, N,N-DIMETHYLACETAMIDE, the N-Methyl pyrrolidone a kind of and toluene wherein or the mixed solvent of dimethylbenzene composition, 20 ∽, the 80% polyimide powder that when beginning to react, just adds polyamic acid weight, this powder has limiting viscosity 0.5 ∽ 1.5dL/g, react the polyamic acid that makes like this and coating polyimide powder, and polyimide molecule is evenly distributed in the polyamic acid solution, polyamic acid is at 150 ℃ of left and right sides cyclodehydrations, what produce behind the cyclodehydration is precipitated as polyimide powder, after filtration, washing and drying obtain polyimide molding powder.Owing to inserted newborn polyimide powder in the slit of original polyimide powder, so that the loose density of the polyimide molding powder that generates is 400 ∽ 500g/L, limiting viscosity is 1.0 ∽ 1.5dL/g.This powder is molded into product for 450 ℃ in 350 ℃ of ∽ under 50MPa ∽ 600MPa pressure, the plastic mould mechanical property is as follows:
Elongation at failure: 〉=5.5%
Unnotched impact strength: 〉=250J/m
Socle girder notched Izod impact strength: 〉=2.6KJ/m
2
Young's modulus 〉=3.0GPa
Polyimide molding powder of the present invention can be by the polycondensation cyclodehydration preparation of aromatic dianhydride and diamines.Promptly select one or more mixture and 4.4 '-diaminodiphenyl oxide (ODA) or mphenylenediamine (MPD) condensation prepared polyamic acid in 50 ℃ of mixed solvents at aprotic polar solvent of 20 ∽ from pyromellitic acid anhydride (PMDA), benzophenone tetracarboxylic dianhydride (BTDA), phenyl ether tetracarboxylic dianhydride (ODPA), bibenzene tetracarboxylic dianhydride (BPDA), that continues prepares polyimide molding powder in 150 ℃ of left and right sides cyclodehydrations.
The used mixed solvent of polycondensation is by aprotic polar solvent, for example: dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP), can choose any one kind of them from them and azeotropic solvent such as toluene or dimethylbenzene mixing composition, wherein azeotropic solvent accounts for 10% ∽ 50% (20% ∽ 40% preferably) of mixed solvent gross weight.
The present invention is at mol ratio aromatic diamine such as adding and two anhydride reactants also add simultaneously and the polyimide powder of the identical or different kind of prepared polyimide powder, add-on is 20 ∽ 80% of polyamic acid weight, and the limiting viscosity of this powder is 0.5 ∽ 1.5dL/g.
Its limiting viscosity of polyimide molding powder η with the inventive method preparation
Int=1.0 ∽ 1.5dL/g, loose density is 400 ∽ 500g/L, its mechanical performance index of product for preparing with this molding powder is:
Tensile strength: 76.2MPa
Elongation at failure: 7.7%
Flexural strength: 103MPa
Modulus in flexure: 3.4GPa
Izod unnotched impact strength: 308J/m
Socle girder notched Izod impact strength: 2.8KJ/m
2
Density 1.42g/cm
3
(4) specific embodiments
In order to implement the present invention better, the spy specifies it, but is not limitation of the present invention.
Example 1
Add 100g (0.5 mole) 4.4 '-diaminodiphenyl oxide, 710.6g N,N-DIMETHYLACETAMIDE, 473.7g dimethylbenzene to the reactor that is equipped with heating and cooling device, agitator, water separator, reflux exchanger, import and export of nitrogen, be heated to about 30 ℃, add 109g (0.5 mole) pyromellitic acid anhydride and 116g PMMI powder (PMDA/ODA) (limiting viscosity η after the stirring and dissolving
Int=0.9dL/g), reach more than the 1dL/g up to solution properties viscosity in 40 ℃ of stirring reactions, be warming up to 144 ℃ then, refluxed 3 hours, water and dimethylbenzene azeotropic that reaction generates steam, then filter the polyimide powder, available heat water washing during the filtration is then in 150 ℃ of dryings 10 hours, continue in 300 ℃ of dryings 3 hours, the result obtains polyimide molding powder, and its limiting viscosity is 1.4dL/g, and loose density is 420g/L.This material High Temperature High Pressure sintering under the high temperature pressure of setting prepares moulded product.The mechanical property of plastic mould is as follows:
Tensile strength 76.2MPa
Elongation at failure 7.7%
Flexural strength 103MPa
Modulus in flexure 3.4GPa
Unnotched impact strength 308J/m
Density 1.42g/cm
3
Example 2
Except that adding 52.25g polydiphenyl ether tetramethyl imide powder (ODPA/ODA) (limiting viscosity is 0.6dL/g), toluene accounts for 20% of mixed solvent gross weight, other are fully identical with example 1, the polyimide molding powder limiting viscosity that the result obtains is that 400g/L. plastic mould mechanical property is an elongation at failure 8% for the 1.3dL/g loose density, unnotched impact strength 330J/m.
Example 3
Except that adding the poly-biphenyl tetracarboxylic imide (BPDA/ODA) (limiting viscosity is 1.45dL/g) of 165g, other is identical with example 1, and the polyimide molding powder limiting viscosity is 1.5dL/g as a result, and loose density is 480g/L.The plastic mould mechanical property is an elongation at failure 7%, unnotched impact strength 300J/m.
Example 4
Add 200g (1.0 moles) 4.4 '-diaminodiphenyl oxide, 1010.3g N,N-DIMETHYLACETAMIDE, 433g dimethylbenzene, be heated to about 30 ℃, add 310g (1.0 moles) phenyl ether tetracarboxylic dianhydrides (ODPA) and 203g PMMI powder (PMDA/ODA) (limiting viscosity η after the stirring and dissolving
Int=0.9dL/g), reach more than the 1dL/g up to solution properties viscosity in 40 ℃ of stirring reactions, be warming up to 144 ℃ then, refluxed 3 hours, finish reaction.The polyimide molding powder limiting viscosity is 1.1dL/g as a result, and loose density is 480g/L.The plastic mould mechanical property is an elongation at failure 8%, tensile strength 80MPa, unnotched impact strength 400J/m, flexural strength 110Mpa.
Example 5
Except that adding 87.2g (0.4 mole) pyromellitic acid anhydride and 31g (0.1 mole) phenyl ether tetracarboxylic dianhydride and 100g (0.5 mole) 4.4 '-diaminodiphenyl oxide in 25 ℃ of reactions, other is identical with example 1, the polyimide molding powder limiting viscosity that the result generates is 1.1dL/g, loose density is 410g/L, and the plastic mould mechanical property is:
Tensile strength: 75MPa
Elongation at failure: 7.8%
Flexural strength: 100MPa
Modulus in flexure: 3.3GPa
Unnotched impact strength: 300J/m
Density: 1.41g/cm
3.
Example 6
100g (0.5 mole) 4.4 '-diaminodiphenyl oxide is dissolved in the mixed solvent of 636.4g N,N-DIMETHYLACETAMIDE and 636.4g dimethylbenzene composition, add 76.3g (0.35 mole) pyromellitic acid anhydride afterwards, inferior powder (PMDA/ODA) (the limiting viscosity η of the poly-equal benzene tetramethyl acyl of 48.3g (0.15 mole) benzophenone tetracarboxylic dianhydride and 54.5g
Int=0.9dL/g), in 50 ℃ of reactions, the polyimide molding powder limiting viscosity that the result generates is that 1.5dL/g, loose density are 500g/L.The plastic mould mechanical property is:
Tensile strength 76.MPa
Elongation at failure is 6.8%
Flexural strength 102MPa
Modulus in flexure 3.5GPa
Unnotched impact strength 260J/m
Density 1.41g/cm
3
Example 7
Add 108.5g (0.35 mole) phenyl ether tetracarboxylic dianhydride (ODPA) and 44.1g (0.15 mole) bibenzene tetracarboxylic dianhydride and 54g (0.5 mole) mphenylenediamine in 20 ℃ of reactions, molding powder (this example) 62g that adds identical mol ratio simultaneously, other is identical with embodiment 4, and the polyimide molding powder limiting viscosity that the result generates is 1.1dL/g loose density 460g/L.The plastic mould mechanical property is:
Tensile strength 78MPa
Elongation at failure is 5.5%
Flexural strength 100MPa
Modulus in flexure 4.0GPa
Unnotched impact strength is 250J/m
Density 1.45g/cm
3
Claims (4)
1, a kind of preparation method of polyimide molding powder is characterized in that:
A) adding when diamines and dianhydride prepare polyamic acid, adding limiting viscosity and be
η
IntThe polyimide powder of the identical or structure inequality of=0.5～1.5DL/g;
B) the preparation polyamic acid is with in the mixed solvent, and toluene or dimethylbenzene account for 10～50 weight % of mixed solvent total amount;
C) etc. the temperature of the aromatic series dianhydride of mol ratio and aromatic diamine reaction is 20～50 ℃, and the cyclodehydration temperature is 110 ℃～150 ℃, after filtration, washing, the dry polyimide molding powder that obtains have limiting viscosity η
Int=1.0～1.5dL/g, loose density is 400～500g/L;
D) from pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride, bibenzene tetracarboxylic dianhydride, choose any one kind of them or two or more mixing, acid anhydride and phenyl ether diamines or mphenylenediamine prepared in reaction polyamic acid, cyclodehydration becomes polyimide molding powder.
2, the preparation method of polyimide molding powder according to claim 1 is characterized in that the polyimide fine powder material amount that is added is polyamic acid weight 20～80 weight %.
3, the preparation method of polyimide molding powder according to claim 1 is characterized in that described mixed solvent is chosen any one kind of them and toluene or dimethylbenzene composition from dimethyl formamide, N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone.
4,, it is characterized in that the ratio that toluene or dimethylbenzene account for mixed solvent is 20～40 weight % according to the described mixed solvent of the preparation method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 03116356 CN1186368C (en) | 2003-04-11 | 2003-04-11 | Method for preparing molding powder of polyimide |
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|---|---|---|---|
| CN 03116356 CN1186368C (en) | 2003-04-11 | 2003-04-11 | Method for preparing molding powder of polyimide |
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| CN1445260A CN1445260A (en) | 2003-10-01 |
| CN1186368C true CN1186368C (en) | 2005-01-26 |
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| CN 03116356 Expired - Lifetime CN1186368C (en) | 2003-04-11 | 2003-04-11 | Method for preparing molding powder of polyimide |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321791C (en) * | 2004-03-30 | 2007-06-20 | 洛阳轴研科技股份有限公司 | Material of porous polyimide holder and molding technique |
| CN101560297B (en) * | 2008-04-14 | 2011-05-18 | 高雄应用科技大学 | Method for preparing polyimide solution and serosity thereof |
| CN103725001B (en) * | 2013-12-27 | 2016-08-17 | 上海市合成树脂研究所 | A kind of preparation method of aerospace low-resistivity polyimide composite material |
| CN104441575B (en) * | 2014-12-29 | 2017-03-29 | 上海市合成树脂研究所 | A kind of forming method of polyimides |
| CN107698794B (en) * | 2016-08-08 | 2020-12-25 | 航天特种材料及工艺技术研究所 | Preparation method of cross-linked polyimide aerogel |
| CN113292726B (en) * | 2021-04-10 | 2023-03-24 | 常州市尚科新材料有限公司 | Polyimide molding powder and preparation method and application thereof |
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Address after: 200235 No. 36, Shanghai, Caobao Road Patentee after: SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS Co.,Ltd. Patentee after: SHANGHAI HUAYI (GROUP) Co. Address before: 200233 No. 36, Shanghai, Caobao Road Patentee before: SHANGHAI Research Institute OF SYNTHETIC RESINS Patentee before: SHANGHAI HUAYI (GROUP) Co. |
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Effective date of registration: 20210225 Address after: No. 1251, Zhulu West Road, Xujing Town, Qingpu District, Shanghai, 201702 Patentee after: SHANGHAI PLASTICS RESEARCH INSTITUTE Co.,Ltd. Patentee after: SHANGHAI HUAYI (Group) Co. Address before: 200235 No. 36, Shanghai, Caobao Road Patentee before: SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS Co.,Ltd. Patentee before: SHANGHAI HUAYI (Group) Co. |
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