CN102199349B - Preparation method of fiber wound high temperature resistant polyimide composite material - Google Patents
Preparation method of fiber wound high temperature resistant polyimide composite material Download PDFInfo
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- CN102199349B CN102199349B CN 201010615939 CN201010615939A CN102199349B CN 102199349 B CN102199349 B CN 102199349B CN 201010615939 CN201010615939 CN 201010615939 CN 201010615939 A CN201010615939 A CN 201010615939A CN 102199349 B CN102199349 B CN 102199349B
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Abstract
The invention discloses a fiber wound high temperature resistant polyimide composite material, and a preparation method thereof. The invention relates to high temperature resistant polyimide composite materials, and preparation methods thereof. In prior arts, because of the poor fluidity and poor technology of polyimide, the preparation technology of high temperature resistant polyimide compositematerials is complicated, and a fiber winding technology is hard to be adopted in the preparation process. With the method provided by the present invention, the problems are solved. The preparation method comprises steps that: the fibers are impregnated with polyimide contained in plastic tanks; the fibers with polyimide are wound on the mold; the materials are heated, imidized and cured according to the procedure; the cured materials are cooled and demolded, such that a finish product is obtained. The preparation method is simple and flexible. With the method of the present invention, a technical difficulty of preparing high temperature resistant polyimide composite materials by using fiber winding technology is solved. The thermolysis temperature Td5 of the prepared high temperature resistant polyimide composite material reaches 556 DEG C under an air atmosphere. The interlaminar shear strength retention rate is 73% under a temperature of 300 DEG C. With a high temperature resistant performance, he material can be used in high-tech fields of national defense, aviation and spaceflight, electric appliance, and medical science.
Description
Technical field
The present invention relates to a kind of preparation method of advanced High Temperature Resistant Polyimide Composites.
Background technology
The problem that prior art exists is following:
Polyimide (Polyimide; Brief note is PI); Flowability is poor, manufacturability is poor; Therefore, be preparing method's complex process of the fibre reinforced composites of matrix with the polyimide, domestic preparation method about advanced High Temperature Resistant Polyimide Composites rests on the moulding process stages such as die press technology for forming and autoclave at present.
Summary of the invention
The objective of the invention is in order to solve because polyimide flows property is poor, manufacturability is poor; The preparing method's complex process that causes advanced High Temperature Resistant Polyimide Composites; And the problem that is difficult to adopt the preparation of fiber winding process, the invention provides the preparation method that a kind of fiber twines the polyimide high temperature-resistant matrix material.
Fiber of the present invention twines the polyimide high temperature-resistant matrix material and is obtained through the fiber winding forming after fixing by polyimide and fiber, and wherein the mass ratio of fiber and polyimide is 1～8:1.
Fiber of the present invention twines the heat decomposition temperature T of polyimide high temperature-resistant matrix material in air atmosphere
d 5Can reach 556 ℃, can reach 73%, show that this matrix material has good resistance to elevated temperatures at 300 ℃ of pyritous interlaminar shear strength retention rates.
Fiber of the present invention twines the polyimide high temperature-resistant composite material and preparation method thereof to be realized through following steps: one, at normal temperatures polyimide is stirred, place in the glue groove of wrapping machine; Two, start wrapping machine, make fiber through glue drill traverse stain polyimide, be wound into then on the mould, wherein the mass ratio of fiber and polyimide is 1～8:1, obtains prefab; Three, will be placed on through the prefab that step 2 obtains and carry out imidization in the curing oven and solidify; Be warming up to 80～150 ℃ and keep 1～3h earlier, then be warming up to 210～250 ℃ and keep 1～3h, be warming up to 280～350 ℃ and keep 1h～3h again; Be warming up to 310～380 ℃ and keep 1.5h～4.5h again; Reduce to room temperature at last, the demoulding then obtains fiber and twines the polyimide high temperature-resistant matrix material.
Polyimide described in the step 1 of the present invention is first-generation polyimide or s-generation polyimide, is the commercially available prod.First-generation polyimide (is designated as PI
f) the life-time service temperature grade of commercially available prod is near 316 ℃, the life-time service temperature grade of s-generation polyimide (being designated as PIz) commercially available prod is near 371 ℃.
Fiber described in the step 2 of the present invention is spun glass, high-strength glass fibre, thomel, aramid fiber, polyparaphenylene's benzo-dioxazole (PBO) fiber, basalt fibre or glasscloth, carbon fibre fabric, aramid fiber fabric, polyparaphenylene's benzo-dioxazole (PBO) fabric or basalt fibre fabric and can be used for other fiber or the glassmat in the matrix material, also is the commercially available prod.
Preparing method of the present invention is simple, has solved the technical barrier that is difficult to make with the fiber winding process advanced High Temperature Resistant Polyimide Composites, and a kind of fiber winding forming polyimide high temperature-resistant matrix material and preparation method thereof is provided.
The fiber of the present invention's preparation twines the polyimide high temperature-resistant matrix material and has good resistance to elevated temperatures, through measuring the heat decomposition temperature T of this matrix material in air atmosphere
d 5Can reach 556 ℃, can reach 73%, show that this matrix material has good resistance to elevated temperatures at 300 ℃ of pyritous interlaminar shear strength retention rates.
The fiber winding forming polyimide high temperature-resistant matrix material that the present invention prepares can be used for high-tech areas such as national defence, aerospace, electronic apparatus, medical science.
Description of drawings
Fig. 1 is a fiber winding process schema of the present invention.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the fiber of this embodiment twines the polyimide high temperature-resistant matrix material and is obtained through the fiber winding forming after fixing by polyimide and fiber, and wherein the mass ratio of fiber and polyimide is 1～8:1.
The fiber of this embodiment twines the heat decomposition temperature T of polyimide high temperature-resistant matrix material in air atmosphere
d 5Can reach 556 ℃, can reach 73% at 300 ℃ of pyritous interlaminar shear strength retention rates, this performance is the performance when adopting s-generation polyimide.Show that this matrix material has good resistance to elevated temperatures.Polyimide is first-generation polyimide or s-generation polyimide in this embodiment.
Embodiment two: this embodiment and embodiment one are different is that the mass ratio of fiber and polyimide is 2～7:1.Other parameter is identical with embodiment one.
Embodiment three: this embodiment and embodiment one are different is that the mass ratio of fiber and polyimide is 4～6:1.Other parameter is identical with embodiment one.
Embodiment four: this embodiment and embodiment one are different is that the mass ratio of fiber and polyimide is 5:1.Other parameter is identical with embodiment one.
Embodiment five: what this embodiment was different with one of embodiment one to four is that polyimide is a first-generation polyimide; Said solidified curing system is: be warming up to 80～150 ℃ and keep 1～3h earlier; Then be warming up to 210～250 ℃ and keep 1～3h; Be warming up to 280～300 ℃ and keep 1h～3h again, be warming up to 310～330 ℃ and keep 1.5h～4.5h again.Other parameter is identical with one of embodiment one to four.
Embodiment six: what this embodiment was different with one of embodiment one to four is that polyimide is a s-generation polyimide; Said solidified curing system is: be warming up to 80～150 ℃ and keep 1～3h earlier; Then be warming up to 210～250 ℃ and keep 1～3h; Be warming up to 300～350 ℃ and keep 1h～3h again, be warming up to 350～380 ℃ and keep 1.5h～4.5h again.Other parameter is identical with one of embodiment one to four.
Embodiment six: the fiber of this embodiment twines the polyimide high temperature-resistant composite material and preparation method thereof to be realized through following steps: one, at normal temperatures polyimide is stirred, place in the glue groove of wrapping machine; Two, start wrapping machine, make fiber through glue drill traverse stain polyimide, be wound into then on the mould, wherein the mass ratio of fiber and polyimide is 1～8:1, obtains prefab; Three, will be placed on through the prefab that step 2 obtains and carry out imidization in the curing oven and solidify; Be warming up to 80～150 ℃ and keep 1～3h earlier, then be warming up to 210～250 ℃ and keep 1～3h, be warming up to 280～350 ℃ and keep 1h～3h again; Be warming up to 310～380 ℃ and keep 1.5h～4.5h again; Reduce to room temperature at last, the demoulding then obtains fiber and twines the polyimide high temperature-resistant matrix material.
The described polyimide of this embodiment step 1 is the commercially available prod, is first-generation polyimide or s-generation polyimide; The described fiber of step 2 also is the commercially available prod.
The preparation method of this embodiment is simple, has solved the technical barrier that is difficult to make with the fiber winding process polyimide high temperature-resistant matrix material, and a kind of fiber winding forming polyimide high temperature-resistant matrix material and preparation method thereof is provided.
The fiber of this embodiment preparation twines the polyimide high temperature-resistant matrix material and has good resistance to elevated temperatures, through measuring the heat decomposition temperature T of this matrix material in air atmosphere
d 5Reach 556 ℃, reach 73%, show that the hot performance of this matrix material and interface performance are good at 300 ℃ of pyritous interlaminar shear strength retention rates.
The preparing method's of this embodiment technical process is as shown in Figure 1, and PI is a polyimide.
Embodiment seven: this embodiment and embodiment six are different is that the mass ratio of fiber and polyimide is 2～7:1 in the step 2.Other step and parameter and embodiment six phase are together.
Embodiment eight: this embodiment and embodiment six are different is that the mass ratio of fiber and polyimide is 4～6:1 in the step 2.Other step and parameter and embodiment six phase are together.
Embodiment nine: this embodiment and embodiment six are different is that the mass ratio of fiber and polyimide is 5:1 in the step 2.Other step and parameter and embodiment six phase are together.
Embodiment ten: what this embodiment was different with one of embodiment six to nine is that fiber is spun glass, thomel, aramid fiber, polyparaphenylene's benzo-dioxazole fiber (pbo fiber), basalt fibre or glasscloth, carbon fibre fabric, aramid fiber fabric, polyparaphenylene's benzo-dioxazole (PBO) fabric or basalt fibre fabric and can be used for other fiber or the fibre felt in the matrix material in the step 2.Other step and parameter are identical with one of embodiment six to nine.
The fiber of this embodiment is the commercially available prod.
Embodiment 11: this embodiment is different with one of embodiment six to ten is to be warming up to 80～150 ℃ and keep 1～3h in the step 3 earlier; Then be warming up to 210～250 ℃ and keep 1～3h; Be warming up to 280～300 ℃ and keep 1h～3h again, be warming up to 310～330 ℃ and keep 1.5h～4.5h again.Other step and parameter are identical with one of embodiment six to ten.
Polyimide adopts first-generation polyimide in this embodiment step 1.
Embodiment 12: this embodiment is different with one of embodiment six to ten is to be warming up to 100～130 ℃ and keep 1.5～2.5h in the step 3 earlier; Then be warming up to 220～240 ℃ and keep 1.5～2.5h; Be warming up to 285～295 ℃ and keep 1.5h～2.5h again, be warming up to 315～325 ℃ and keep 3.8h～4.2h again.Other step and parameter are identical with one of embodiment six to ten.
Polyimide adopts first-generation polyimide in this embodiment step 1.
Embodiment 13: this embodiment is different with one of embodiment six to ten is to be warming up to 120 ℃ and keep 2h in the step 3 earlier, then is warming up to 230 ℃ and keep 2h, is warming up to 290 ℃ and keep 2h again, is warming up to 320 ℃ and keep 4h again.Other step and parameter are identical with one of embodiment six to ten.
Polyimide adopts first-generation polyimide in this embodiment step 1.
Embodiment 14: this embodiment is different with one of embodiment six to ten is to be warming up to 80～150 ℃ and keep 1～3h in the step 3 earlier; Then be warming up to 210～250 ℃ and keep 1～3h; Be warming up to 300～350 ℃ and keep 1h～3h again, be warming up to 350～380 ℃ and keep 1.5h～4.5h again.Other step and parameter are identical with one of embodiment six to ten.
Polyimide adopts s-generation polyimide in this embodiment step 1.
Embodiment 15: this embodiment is different with one of embodiment six to ten is to be warming up to 100～130 ℃ and keep 1.5～2.5h in the step 3 earlier; Then be warming up to 220～240 ℃ and keep 1.5～2.5h; Be warming up to 310～330 ℃ and keep 1.5h～2.5h again, be warming up to 360～370 ℃ and keep 3.8h～4.2h again.Other step and parameter are identical with one of embodiment six to ten.
Polyimide adopts s-generation polyimide in this embodiment step 1.
Embodiment 16: this embodiment is different with one of embodiment six to ten is to be warming up to 120 ℃ and keep 2h in the step 3 earlier, then is warming up to 230 ℃ and keep 2h, is warming up to 320 ℃ and keep 2h again, is warming up to 365 ℃ and keep 4h again.Other step and parameter are identical with one of embodiment six to ten.
Polyimide adopts s-generation polyimide in this embodiment step 1.
Embodiment 17: the fiber of this embodiment twines the polyimide high temperature-resistant composite material and preparation method thereof to be realized through following steps: one, at normal temperatures s-generation polyimide is stirred, place in the glue groove of wrapping machine; Two, start wrapping machine, make high-strength glass fibre through glue drill traverse stain s-generation polyimide, be wound into then on the mould, wherein the mass ratio of high-strength glass fibre and s-generation polyimide is 3:1, obtains prefab; Three, will be placed on through the prefab that step 2 obtains and carry out imidization in the curing oven and solidify; Be warming up to 120 ℃ and keep 2h earlier, then be warming up to 230 ℃ and keep 2h, be warming up to 320 ℃ and keep 2h again; Be warming up to 365 ℃ and keep 4h again; Reduce to room temperature at last, the demoulding then obtains fiber and twines the polyimide high temperature-resistant matrix material.
It is that high-strength glass fibre twines advanced High Temperature Resistant Polyimide Composites that the fiber of this embodiment twines the polyimide high temperature-resistant matrix material, and (brief note is GF to be designated as high-strength glass fibre/composite polyimide material
S/ PIz).
High-strength glass fibre/the composite polyimide material of this embodiment preparation has good resistance to elevated temperatures, through measuring the heat decomposition temperature T of high-strength glass fibre/composite polyimide material in air atmosphere
d 5Reaching 546 ℃, is 72% at 300 ℃ of pyritous interlaminar shear strength retention rates, shows that the hot performance of high-strength glass fibre/composite polyimide material and interface performance are good.
High-strength glass fibre/composite polyimide material that this embodiment prepares is the preferred material of high-tech areas such as national defence, aerospace, electronic apparatus, medical science.
Embodiment 18: the fiber of this embodiment twines the polyimide high temperature-resistant composite material and preparation method thereof to be realized through following steps: one, at normal temperatures s-generation polyimide is stirred, place in the glue groove of wrapping machine; Two, start wrapping machine, make thomel through glue drill traverse stain s-generation polyimide, be wound into then on the mould, wherein the mass ratio of thomel and s-generation polyimide is 3:1, obtains prefab; Three, will be placed on through the prefab that step 2 obtains and carry out imidization in the curing oven and solidify; Be warming up to 120 ℃ and keep 2h earlier, then be warming up to 230 ℃ and keep 2h, be warming up to 320 ℃ and keep 2h again; Be warming up to 370 ℃ and keep 4h again; Reduce to room temperature at last, the demoulding then obtains thomel and twines the polyimide high temperature-resistant matrix material.
It is that thomel twines advanced High Temperature Resistant Polyimide Composites that the thomel of this embodiment twines the polyimide high temperature-resistant matrix material, is designated as carbon fiber/polyamide imines matrix material.
The carbon fiber/polyamide imines matrix material of this embodiment preparation has good resistance to elevated temperatures, through measuring the heat decomposition temperature T of carbon fiber/polyamide imines matrix material in air atmosphere
d 5Reach 556 ℃.
Claims (6)
1. fiber twines the preparation method of polyimide high temperature-resistant matrix material; It is characterized in that fiber twines the polyimide high temperature-resistant composite material and preparation method thereof and realizes through following steps: one, at normal temperatures polyimide is stirred, place in the glue groove of wrapping machine; Two, start wrapping machine, make fiber through glue drill traverse stain polyimide, be wound into then on the mould, wherein the mass ratio of fiber and polyimide is 1～8:1, obtains prefab; Three, will be placed on through the prefab that step 2 obtains and carry out imidization in the curing oven and solidify; Be warming up to 80～150 ℃ and keep 1～3h earlier, then be warming up to 210～250 ℃ and keep 1～3h, be warming up to 280～350 ℃ and keep 1h～3h again; Be warming up to 310～380 ℃ and keep 1.5h～4.5h again; Reduce to room temperature at last, the demoulding then obtains fiber and twines the polyimide high temperature-resistant matrix material.
2. fiber according to claim 1 twines the preparation method of polyimide high temperature-resistant matrix material, it is characterized in that polyimide is first-generation polyimide or s-generation polyimide in the step 1.
3. fiber according to claim 1 twines the preparation method of polyimide high temperature-resistant matrix material, it is characterized in that the mass ratio of fiber and polyimide is 2～7:1 in the step 2.
4. the preparation method of twining the polyimide high temperature-resistant matrix material according to claim 1,2 or 3 described fibers is characterized in that fiber is spun glass, thomel, aramid fiber, polyparaphenylene's benzo-dioxazole fiber or basalt fibre in the step 2.
5. the preparation method of twining the polyimide high temperature-resistant matrix material according to claim 1,2 or 3 described fibers; It is characterized in that being warming up to earlier in the step 3 80～150 ℃ and keep 1～3h; Then be warming up to 210～250 ℃ and keep 1～3h; Be warming up to 280～300 ℃ and keep 1h～3h again, be warming up to 310～330 ℃ and keep 1.5h～4.5h again, wherein polyimide is a first-generation polyimide in the step 1.
6. the preparation method of twining the polyimide high temperature-resistant matrix material according to claim 1,2 or 3 described fibers; It is characterized in that being warming up to earlier in the step 3 80～150 ℃ and keep 1～3h; Then be warming up to 210～250 ℃ and keep 1～3h; Be warming up to 300～350 ℃ and keep 1h～3h again, be warming up to 350～380 ℃ and keep 1.5h～4.5h again, wherein polyimide is a s-generation polyimide in the step 1.
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Cited By (1)
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| CN115521613A (en) * | 2021-06-25 | 2022-12-27 | 中微半导体设备(上海)股份有限公司 | Heat-conducting and electric-conducting elastic composite material, preparation method thereof and semiconductor processing device |
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| CN103525087A (en) * | 2013-08-15 | 2014-01-22 | 上海舟汉纤维材料科技有限公司 | Method for preparing poly-p-phenylene benzoxazole (PBO) fiber reinforced resin based composite material |
| CN107033592A (en) * | 2016-12-12 | 2017-08-11 | 德阳力久云智知识产权运营有限公司 | A kind of polyimide resin enhancing composite and preparation method thereof |
| CN108752929A (en) * | 2018-05-04 | 2018-11-06 | 常州储能材料与器件研究院 | A kind of basalt fiber composite material and preparation method thereof |
| CN113334795A (en) * | 2021-05-10 | 2021-09-03 | 宋阳 | Process preparation method of polyurethane tower pole |
| CN114103077B (en) * | 2021-11-19 | 2023-05-09 | 西华大学 | Hydrogen storage cylinder and preparation method thereof |
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| CN115521613A (en) * | 2021-06-25 | 2022-12-27 | 中微半导体设备(上海)股份有限公司 | Heat-conducting and electric-conducting elastic composite material, preparation method thereof and semiconductor processing device |
| CN115521613B (en) * | 2021-06-25 | 2024-03-12 | 中微半导体设备(上海)股份有限公司 | Heat-conducting and electricity-conducting elastic composite material, preparation method thereof and semiconductor processing device |
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