CN101412849A - Preparation of three-dimensional orthogonal woven fabric reinforced thermoplastic polyimide resin composite material - Google Patents
Preparation of three-dimensional orthogonal woven fabric reinforced thermoplastic polyimide resin composite material Download PDFInfo
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- CN101412849A CN101412849A CNA2008102035029A CN200810203502A CN101412849A CN 101412849 A CN101412849 A CN 101412849A CN A2008102035029 A CNA2008102035029 A CN A2008102035029A CN 200810203502 A CN200810203502 A CN 200810203502A CN 101412849 A CN101412849 A CN 101412849A
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Abstract
The invention relates to a method for preparing a thermoplastic polyimide composite material through strengthening three-dimensional orthogonal woven fabric. The method comprises the following steps: (1) the three-dimensional orthogonal woven fabric is taken out, weighed, sorted, leveled; a polyamic acid solution is poured to submerge the woven fabric; and the woven fabric with the solution is subjected to vacuum deaeration in a vacuum oven; (2) the woven fabric is taken out; residual liquid on the surface of the woven fabric is rolled; the woven fabric is sorted, is put to the oven again, is vacuumized and is subjected to gradient temperature rise to realize primary imidization; (3) the sample is solidified, cleaned and dried; according to the step one and the step two, the sample is continuously soaked in the polyamic acid solution for five times totally; and (4) the sample is subjected to hot rolling and molding through a plate vulcanizing machine to obtain the compact thermoplastic polyimide composite material strengthened by the three-dimensional orthogonal woven fabric. The method solves the problem that after single gum dipping, a prefabricated member has low content of resin caused by the volatilization of a small molecular solvent.
Description
Technical field
The invention belongs to the thermoplastic polyimide preparation field, particularly relate to a kind of preparation method of three-dimensional orthogonal woven fabric enhanced thermoplastic polyimide composite material.
Background technology
Thermoplastic polyimide adopts aromatic dianhydride and the aromatic diamines a series of step-growth polymerization reaction in-situ preparing in polar solvent to form usually.Usually in two steps: the first step is to generate the polyamic acid oligopolymer.This reaction is normally carried out in the scope of room temperature to 150 ℃, needs to remove moisture, ethanol and solvent etc. simultaneously.Second step was an imidization, removed simultaneously and anhydrated or ethanol.The temperature of imidization reaction is greatly about 150 to 316 ℃.When the preparation matrix material, use intermediate product polyamic acid preimpregnation three-dimensional orthogonal fabric to obtain prepreg, hot-imide removes solvent and small molecules then.Because the solvent that uses, as N-Methyl pyrrolidone (NMP) and N,N-DIMETHYLACETAMIDE (DMAC), boiling point is higher, brought difficulty for the removal of matrix material course of processing solvent, simultaneously because the volatilization and micromolecular the removing of a large amount of solvents are shunk pre-soaked resin in a large number, the inequality owing to be heated everywhere produces string stress, and high porosity appears in matrix material easily that obtain.This is the main drawback of this class way.
In addition, in the imidization reaction process in second step, molecular chain is elongated, and the viscosity of polymkeric substance increases, and in order to obtain fine and close matrix material, must exert pressure in this stage.The key of condensation polymer type composite polyimide material processing and preparing just is to remove before the compacting or in the compacting process by product and the residual solvent in the dereaction.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of three-dimensional orthogonal woven fabric enhanced thermoplastic polyimide composite material has solved behind the single impregnation because the small molecules solvent evaporates causes the extremely low problem of resin content in the prefabricated component.
The preparation method of three-dimensional orthogonal woven fabric enhanced thermoplastic polyimide composite material of the present invention comprises step:
(1) gets three-dimensional orthogonal woven fabric, weigh, put into container after arrangement is flat, pour the polyamic acid solution in 1 hour after the polymerization into, until flooding fabric; The container that fills fabric is put into vacuum drying oven, vacuum 0.07MPa-0.08MPa deaeration, the auxiliary fabric that soaks into, leave standstill 15～30min to there not being new bubble to emerge, then strengthen vacuum tightness to 0.08MPa-0.09MPa, leave standstill 15～30min, up to there not being new bubble to emerge, strengthen vacuum tightness 0.09MPa-0.1MPa, leave standstill 15～30min and obviously reduce up to the bubble of emerging;
(2) take out the fabric that is immersed in the polyamic acid solution, roll the fabric face excess liquid, after the arrangement, be reentered in the baking oven, vacuumize 0.08MPa-0.09MPa and carry out gradient increased temperature, realize preliminary imidization;
(3) after the sample solidifies, clean oven dry, and continue sample is soaked polyamic acid solution according to preceding described step (1) and (2), altogether sample is soaked polyamic acid solution five times, in this process, note continuing to increase vacuum tightness fabric and resin are as far as possible fully soaked into;
(4) to through soaking three-dimensional orthogonal woven fabric enhanced composite polyimide material behind the polyamic acid solution for five times behind 256 ℃, 5MPa, maintenance 0.5～1.5h, again through 300 ℃, 5MPa, maintenance 0.5～1.5h, carry out the vulcanizing press hot-roll forming, get fine and close three-dimensional orthogonal fabric enhanced thermoplastic polyimide composite material.
Three-dimensional orthogonal woven fabric in the described step (1) is that a kind of process three-dimensional orthogonal loom in any high-performance fiber (as glass fibre, aramid fiber, basalt fibre) is weaved the fabric that forms, thickness 3mm or 5mm, size 20cm * 30cm.
The preparation of the polyamic acid in the described step (1) is: polymerization reaction monomer is 3,3 ＇, and 4,4 ＇-two phenyl ketone tetracid acid anhydrides and 4,4 ＇-dianiline base ether is taked the mole proportioning of 1.02:1; Earlier 4,4 ＇-dianiline base ether is dissolved in N, in the N dimethyl formamide solvent, after stirring and dissolving is complete, adds 3,3 stand-by in moisture eliminator ＇ in three batches, 4,4 ＇-two phenyl ketone tetracid acid anhydrides, normal temperature reaction down got polyamic acid after 6 hours.
Gradient increased temperature sequencing in the described step (2) is 80 ℃ of insulation 1.5～2.5h, 120 ℃ of insulation 0.5～1.5h, 150 ℃ of insulation 0.5～1.5h, 180 ℃ of insulation 0.5～1.5h.
The present invention in order to improve the impregnation rate, must constantly replenish the mode that resin promptly adopts repeatedly impregnation in to the three-dimensional orthogonal woven fabric immersing glue process, and investigates the influence of impregnation number of times to the impregnation rate.
Beneficial effect:
Weak point simple to operate, consuming time, efficient height, the composite property of preparation is good.
Description of drawings
Fig. 1 is three-dimensional orthogonal fabric reinforced composite pretreatment process figure;
Fig. 2 is the moulding schema of three-dimensional orthogonal fabric reinforced composite.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
The monomer that polyreaction is used is 3,3 ＇, 4,4 ＇-two phenyl ketone tetracid acid anhydrides (BTDA) and 4,4 ＇-dianiline base ether (ODA) is taked the mole proportioning of 1.02:1, earlier ODA is dissolved in N, in N-dimethyl formamide (DMF) solvent, after stirring and dissolving is complete, add BTDA stand-by in the moisture eliminator in three batches.After 6 hours, obtain yellow polyamic acid (PAA), refrigeration, stand-by.
Getting thickness is the three-dimensional orthogonal basalt fabric of 3mm, puts into appropriate containers after fabric is weighed, and pours polyamic acid solution into fabric is immersed.Put into vacuum drying oven, adjusting vacuum tightness is 0.07-0.08MPa, and solution begins deaeration, soaks into fabric gradually, kept 15 minutes, and continued to heighten vacuum tightness, kept 15 minutes, regulate vacuum tightness at last to more than the 0.1MPa to 0.09MPa, kept 15 minutes, and transferred to normal pressure, take out container.
Take out the fabric of preimpregnation, remove the unnecessary polyamic acid in surface, be reentered in the baking oven, be evacuated to 0.08-0.09MPa, make solvent evaporates abundant, realize the preliminary imidization of polyamic acid according to schema 1 pre-treatment that heats up.
Behind the hot-imide, weigh, and calculate the impregnation rate.Downcut sample segment, cleaning, drying, two portions sample is all weighed, remaining sample is put into container, pour resin into, as previously mentioned, vacuumize auxiliary impregnation for the second time, and constantly heighten vacuum tightness fabric and resin are as far as possible fully soaked into, transfer to normal pressure after stablizing, take out fabric, roll unnecessary polyamic acid resin, be reentered into baking oven, be evacuated to 0.08～0.09MPa, remove solvent by Fig. 1 flow process intensification pre-treatment, realize preliminary imidization.Soak altogether five times with identical way, all take off at every turn sample a little.Suppose fully evenly impregnation of sample, calculate the gluing rate according to impregnation weight difference before and after every sample.The basalt fibre fabric reinforcement composite polyimide material of different impregnation number of times through the vulcanizing press hot-roll forming, naturally cools to room temperature by flow process shown in Figure 2, just obtains fine and close basalt fibre three-dimensional orthogonal fabric and strengthens composite polyimide material.
In order to detect the impregnation number of times to matrix material machinery Effect on Performance, according to GB/T 1449-1983, test 3mm thickness, the bending property of the three-dimensional woven basalt fibre fabric reinforced composite of the different impregnation number of times of process is as follows.
The bending property of the different impregnation number of times of polyimide-based composite material
Claims (4)
1. the preparation method of a three-dimensional orthogonal woven fabric enhanced thermoplastic polyimide composite material comprises step:
(1) gets three-dimensional orthogonal woven fabric, weigh, put into container after arrangement is flat, pour polymerization 1 hour into interior polyamic acid solution, until flooding fabric; The container that fills fabric is put into vacuum drying oven, vacuum 0.07MPa-0.08MPa deaeration, the auxiliary fabric that soaks into, leave standstill 15～30min to there not being new bubble to emerge, then strengthen vacuum tightness to 0.08MPa-0.09MPa, leave standstill 15～30min, up to there not being new bubble to emerge, strengthen vacuum tightness 0.09MPa-0.1MPa, leave standstill 15～30min;
(2) take out the fabric that is immersed in the polyamic acid solution, roll the fabric face excess liquid, after the arrangement, be reentered in the baking oven, vacuumize 0.08MPa-0.09MPa and carry out gradient increased temperature, realize preliminary imidization;
(3) after the sample solidifies, clean, dry, and continue sample is soaked polyamic acid solution, altogether sample is soaked polyamic acid solution five times according to preceding described step (1) and (2);
(4) to through soaking three-dimensional orthogonal woven fabric enhanced composite polyimide material behind the polyamic acid solution for five times behind 250 ℃, 5MPa, maintenance 0.5～1.5h, again through 300 ℃, 5MPa, maintenance 0.5～1.5h, carry out the vulcanizing press hot-roll forming, get fine and close three-dimensional orthogonal fabric enhanced thermoplastic polyimide composite material.
2. the preparation method of three-dimensional orthogonal woven fabric enhanced thermoplastic polyimide composite material according to claim 1, it is characterized in that: the three-dimensional orthogonal woven fabric in the described step (1) is that glass fibre, aramid fiber or basalt fibre are weaved the fabric that forms through the three-dimensional orthogonal loom, thickness 3mm or 5mm, size 20cm * 30cm.
3. the preparation method of three-dimensional orthogonal woven fabric enhanced thermoplastic polyimide composite material according to claim 1, it is characterized in that: the polymerization reaction monomer that is prepared as of the polyamic acid in the described step (1) is 3,3 ', 4,4 '-two phenyl ketone tetracid acid anhydrides and 4,4 '-dianiline base ether, the mol ratio proportioning of pressing 1.02:1; Earlier 4,4 '-dianiline base ether is dissolved in N, in N-solvent dimethylformamide, stirring and dissolving fully after, add in three batches stand-by 3,3 in the moisture eliminator ', 4,4 '-two phenyl ketone tetracid acid anhydrides, normal temperature reaction down got polyamic acid after 6 hours.
4. the preparation method of three-dimensional orthogonal woven fabric enhanced thermoplastic polyimide composite material according to claim 1 is characterized in that: the gradient increased temperature sequencing in the described step (2) is 80 ℃ of insulation 1.5～2.5h, 120 ℃ of insulation 0.5～1.5h, 150 ℃ of insulation 0.5～1.5h, 180 ℃ of insulation 0.5～1.5h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585966B (en) * | 2009-06-17 | 2011-12-14 | 东华大学 | Production method of three-dimensional orthogonal woven fabric reinforced PMR type polyimide composite material |
| CN106398212A (en) * | 2016-12-12 | 2017-02-15 | 德阳力久云智知识产权运营有限公司 | Polyimide resin composite material and preparation method thereof |
| CN108299825A (en) * | 2018-03-23 | 2018-07-20 | 航天特种材料及工艺技术研究所 | Compound electromagnetic wave transparent material of fire resistant resin base and preparation method thereof when a kind of long |
| 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 |
| CN109370216A (en) * | 2018-08-22 | 2019-02-22 | 中国人民解放军国防科技大学 | Three-dimensional fiber fabric reinforced polyimide resin-based composite material and preparation method thereof |
| CN109468846A (en) * | 2018-11-06 | 2019-03-15 | 贵州理工学院 | A kind of aramid fiber surface grafting processing method |
-
2008
- 2008-11-27 CN CN2008102035029A patent/CN101412849B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585966B (en) * | 2009-06-17 | 2011-12-14 | 东华大学 | Production method of three-dimensional orthogonal woven fabric reinforced PMR type polyimide composite material |
| CN106398212A (en) * | 2016-12-12 | 2017-02-15 | 德阳力久云智知识产权运营有限公司 | Polyimide resin composite material and preparation method thereof |
| CN108299825A (en) * | 2018-03-23 | 2018-07-20 | 航天特种材料及工艺技术研究所 | Compound electromagnetic wave transparent material of fire resistant resin base and preparation method thereof when a kind of long |
| 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 |
| CN109370216A (en) * | 2018-08-22 | 2019-02-22 | 中国人民解放军国防科技大学 | Three-dimensional fiber fabric reinforced polyimide resin-based composite material and preparation method thereof |
| CN109370216B (en) * | 2018-08-22 | 2022-01-28 | 中国人民解放军国防科技大学 | Three-dimensional fiber fabric reinforced polyimide resin-based composite material and preparation method thereof |
| CN109468846A (en) * | 2018-11-06 | 2019-03-15 | 贵州理工学院 | A kind of aramid fiber surface grafting processing method |
| CN109468846B (en) * | 2018-11-06 | 2020-12-25 | 贵州理工学院 | Aramid fiber surface grafting treatment method |
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