CN101580687B - Fluorenyl-containing polyimide high temperature-resistant adhesive and preparation method thereof - Google Patents
Fluorenyl-containing polyimide high temperature-resistant adhesive and preparation method thereof Download PDFInfo
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- CN101580687B CN101580687B CN2009100723141A CN200910072314A CN101580687B CN 101580687 B CN101580687 B CN 101580687B CN 2009100723141 A CN2009100723141 A CN 2009100723141A CN 200910072314 A CN200910072314 A CN 200910072314A CN 101580687 B CN101580687 B CN 101580687B
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Abstract
The invention relates to a high temperature-resistant adhesive and a preparation method thereof, in particular to flourenyl-containing polyimide (PI) high temperature-resistant adhesive and a preparation method thereof. The invention solves the problem that the bonding strength of the existing organic adhesive is not high at a high temperature, particularly at 400 DEG C. The flourenyl-containing PI high temperature-resistant adhesive of the invention is prepared from soluble fluorenyl-containing PI, N-methyl-2-pyrrolidone (NMP), tertiary amine stabilizers and water absorbent. The preparation method of the invention comprises the following step: evenly mixing the soluble fluorenyl-containing PI, the NMP, the tertiary amine stabilizers and the water absorbent to obtain the flourenyl-containing PI high temperature-resistant adhesive. The bonding strength of the flourenyl-containing PI high temperature-resistant adhesive can reach 6.5MPa and the invention is used for bonding structural members at the temperature of 400 DEG C.
Description
Technical field
The present invention relates to a kind of polyimide high temperature-resistant adhesive and preparation method thereof.
Background technology
Develop rapidly along with high-tech, people require increasingly highly to material, and especially the application requiring of non-metallic material enlarges day by day, and therefore, the restriction that is connected to become between structural part or the non-structural part much has the bottleneck that the excellent properties material is used.Tackiness agent can partly replace traditional welding, riveted joint or bolt and connect as the important material that material connects that is used for, even can be used for can't or riveting the position that connects with welding at all.Study on making adhesives is used and is received much concern day by day.
Because the requirement of high speed, hypogravity makes to the working temperature requirement of thermotolerance tackiness agent also increasingly high.The temperature resistant grade of epoxyn, synvaren can't meet the demands, and fragrant heterocyclic polymer such as polyimide use as high-temperature resistance adhesive and receive increasing concern.
Polyimide (PI) is the aromatic heterocycle polymer material that last century, early sixties was at first developed by du pont company, has good temperature resistance ability and good mechanics, dielectric and radiation resistance.It becomes field indispensable material such as space flight, aviation, machinery, chemical industry, microelectronics as structured material or as functional material, has broad application prospects, and use still receives great restriction but it is as tackiness agent." Chinese patent: 00120274.x " reported the polyimide that can be used for high-temperature adhesives; It adopts different diamines and dianhydride or its mixture staple as synthesis of polyimides presoma-polyamic acid; Through adding part tertiary amine or quaternary amine; Break chain-like structure, reduced the interchain tap density, increased the fusing suitability of polyimide.The insulation tape that makes with this polyamic acid or polyimide can carry out bondingly not being higher than under 450 ℃, but because it is to carry out bondingly through fusing under the hot conditions, must cause high temperature bonding intensity not high, and its use temperature is only about 300 ℃.
Summary of the invention
The objective of the invention is in order to solve existing organic adhesion agent at high temperature, especially the not high problem of cohesive strength under 400 ℃ of conditions the invention provides a kind of fluorenyl-containing polyimide high temperature-resistant adhesive and preparation method thereof.
Fluorenyl-containing polyimide high temperature-resistant adhesive of the present invention is mainly processed by 10～20 parts of solubility fluorenyl-containing polyimides, 60～80 parts of N SL 1332s, 1～5 part of tertiary amines stablizer and 5～10 parts of water-retaining agents by ratio of quality and the number of copies.The preparation method of fluorenyl-containing polyimide high temperature-resistant adhesive of the present invention is: take by weighing 10～20 parts of solubility fluorenyl-containing polyimides, 60～80 parts of N SL 1332s, 1～5 part of tertiary amines stablizer and 5～10 parts of water-retaining agents respectively by ratio of quality and the number of copies; Then fluorenyl-containing polyimide is added mixed dissolution in the N SL 1332; Add stablizer and water-retaining agent again; Stir, promptly get fluorenyl-containing polyimide high temperature-resistant adhesive.
Fluorenyl-containing polyimide high temperature-resistant adhesive Heat stability is good of the present invention; Initial heat decomposition temperature is up to 470 ℃; Second-order transition temperature (Tg) is about 300 ℃, and the high temperature cohesive strength of tackiness agent is high, and shearing resistance of 400 ℃ of following its bonding carbon steels can reach 6.5MPa.Preparing method's technology of fluorenyl-containing polyimide high temperature-resistant adhesive of the present invention is simple, operates simple and easyly, and the fluorenyl-containing polyimide high temperature-resistant adhesive thermal stability that obtains is good, and high temperature cohesive strength is big.The present invention will have the good fluorenyl-containing polyimide of solubility property of cast structural fluorenyl and introduce in the tackiness agent; Make the generation of having avoided bubble in the splicing process to greatest extent; Cementitious safety and weather resistance have been improved; Shearing resistance of its bonding carbon steel can reach 6.5MPa under 400 ℃, can satisfy the requirement of high temperature bonding.
Description of drawings
Fig. 1 is the infrared spectrogram that embodiment eight step 1 to four synthetic contain the fluorenyl polyamic acid; Fig. 2 is the infrared spectrogram of embodiment eight step 1 to five synthetic fluorenyl-containing polyimides; Fig. 3 is thermal weight loss (TG) analysis of the fluorenyl-containing polyimide high temperature-resistant adhesive of embodiment 23 preparations; Fig. 4 is heat machinery (DMA) spectrogram of the fluorenyl-containing polyimide high temperature-resistant adhesive of embodiment 23 preparations; Fig. 5 is thermal weight loss (TG) analysis of the fluorenyl-containing polyimide high temperature-resistant adhesive of embodiment 24 preparations; Fig. 6 is heat machinery (DMA) spectrogram of the fluorenyl-containing polyimide high temperature-resistant adhesive of embodiment 24 preparations.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: this embodiment fluorenyl-containing polyimide high temperature-resistant adhesive is mainly processed by 10～20 parts of solubility fluorenyl-containing polyimides, 60～80 parts of N SL 1332s, 1～5 part of tertiary amines stablizer and 5～10 parts of water-retaining agents by ratio of quality and the number of copies.
The fluorenyl-containing polyimide high temperature-resistant adhesive thermal stability is good in this embodiment; Initial heat decomposition temperature is up to 470 ℃; Second-order transition temperature is about 300 ℃; And the high temperature cohesive strength of fluorenyl-containing polyimide high temperature-resistant adhesive is high, and shearing resistance of 400 ℃ of following its bonding carbon steels can reach 6.5MPa.
Embodiment two: this embodiment and embodiment one are different is that the structural formula of fluorenyl-containing polyimide is:
wherein; M, n are the unitary mole number of repeating structure; M: n=(1/9～9): 1, its weight-average molecular weight is 80000～150000.Other parameter is identical with embodiment one.
The solubility property of fluorenyl-containing polyimide is good in this embodiment.
Table 1 is the solubility property of fluorenyl-containing polyimide in the embodiment two.
This embodiment carries out the solubility property test to fluorenyl-containing polyimide, and the result sees table 1.Wherein, in the table ++ expression is dissolving fully, and+expression is partly dissolved, and-expression is soluble.
Table 1
| m∶n | N ' N-N,N-DIMETHYLACETAMIDE | The N SL 1332 | DMSO 99.8MIN. | N ' dinethylformamide | THF | Toluene | Methyl alcohol |
| 1∶9 | - | + | - | ?- | - | - | - |
| 3∶7 | - | ++ | - | ?- | - | - | - |
| 5∶5 | + | ++ | - | ?+ | - | - | - |
| 7∶3 | + | ++ | + | ?+ | - | - | - |
| 9∶1 | + | ++ | + | ?+ | + | + | - |
Visible by table 1, the fluorenyl-containing polyimide solubility property is good, dissolve in the organic solvent commonly used, and like toluene, N, N '-N, N, N '-N,N-DIMETHYLACETAMIDE, N SL 1332, DMSO 99.8MIN. or THF.Wherein, the solubility property in the N SL 1332 is best.
Embodiment three: what this embodiment was different with embodiment one or two is that stablizer is triethylamine, tripropyl amine or diethylammonium methylamine.Other parameter is identical with embodiment one or two.
Embodiment four: what this embodiment and embodiment one to three were different is that water-retaining agent is 4A molecular sieve or 100～300 order lime powders.Other parameter is identical with embodiment one to three.
Embodiment five: what this embodiment and embodiment one to four were different is that a kind of fluorenyl-containing polyimide high temperature-resistant adhesive also comprises 1～5 part bismaleimides by ratio of quality and the number of copies.Other parameter is identical with embodiment one to four.
Bismaleimides is the commercially available prod in this embodiment.
Embodiment six: what this embodiment and embodiment one to five were different is that a kind of fluorenyl-containing polyimide high temperature-resistant adhesive is processed by 20 parts of solubility fluorenyl-containing polyimides, 2 parts of bismaleimidess, 70 parts of N SL 1332s, 2 parts of tertiary amines stablizers and 6 parts of water-retaining agents by ratio of quality and the number of copies.Other parameter is identical with embodiment one to five.
Embodiment seven: the preparation method of this embodiment fluorenyl-containing polyimide high temperature-resistant adhesive is: take by weighing 10～20 parts of solubility fluorenyl-containing polyimides, 60～80 parts of N SL 1332s, 1～5 part of tertiary amines stablizer and 5～10 parts of water-retaining agents respectively by ratio of quality and the number of copies; Then the solubility fluorenyl-containing polyimide is added mixed dissolution in the N SL 1332; Add stablizer and water-retaining agent again; Stir, promptly get fluorenyl-containing polyimide high temperature-resistant adhesive.
Preparing method's technology of this embodiment fluorenyl-containing polyimide high temperature-resistant adhesive is simple; Operate simple and easy; The fluorenyl-containing polyimide high temperature-resistant adhesive thermal stability that obtains is good, and initial heat decomposition temperature is up to 470 ℃, and second-order transition temperature is about 300 ℃; And the high temperature cohesive strength of fluorenyl-containing polyimide high temperature-resistant adhesive is high, and shearing resistance of 400 ℃ of following its bonding carbon steels can reach 6.5MPa.The solvability energy consumption that the present invention will have a cast structural fluorenyl gets very the fluorenyl polyimide and introduces in the tackiness agent; Make the generation of having avoided bubble in the splicing process to greatest extent; Cementitious safety and weather resistance have been improved; Shearing resistance of its bonding carbon steel can reach 6.5MPa under 400 ℃, can satisfy the requirement of high temperature bonding.
Embodiment eight: this embodiment and embodiment seven are different is that the structural formula of fluorenyl-containing polyimide is:
Wherein, m, n are the unitary mole number of repeating structure, m: n=(1/9～9): 1, and its weight-average molecular weight is 80000～150000; Be through the following steps synthetic: one, 3～4 parts of Fluorenones, 15 parts of aniline and 1 part of methanesulfonic are put into reactor drum by ratio of quality and the number of copies; Stirring is warming up to 150～180 ℃, and insulation reaction 10h～14h leaves standstill 12h～30h after in reactor drum, adding 10 parts of ethanol and 1 part of triethylamine by ratio of quality and the number of copies again; Suction filtration then; Again through re-crystallizing in ethyl acetate, obtain 9,9 after the vacuum-drying '-two (4-aminophenyl) fluorenes; Two, with step 1 obtain 9,9 '-two (4-aminophenyl) fluorenes and 4 (1/9～9) in molar ratio: 1 joins in the reaction vessel and mixes, both mixtures; Three, in reaction vessel, add non-proton type polar solvent, stirring and dissolving gets clear solution, in wherein non-proton type polar solvent and the step 29,9 '-ratio of two (4-aminophenyl) fluorenes and 4 mixture is 4L～7L: 1mol; Four, the solution that step 3 is obtained is put into ice bath and is cooled to 0 ℃, in whipped state downhill reaction container, add 3,3 then ' and, 4; 4 '-after oxygen supports adjacent pyromellitic dianhydride, continue stirring reaction 3-5h, obtain containing the fluorenyl polyamic acid, wherein; 3,3 ', 4; 4 '-oxygen supports in adjacent pyromellitic dianhydride and the step 29,9 '-mol ratio of two (4-aminophenyl) fluorenes and 4 mixture is 1: 1; Five, the polyamic acid that step 4 is obtained is put into baking oven and is warming up to 200 ℃, is warming up to 250 ℃ behind constant temperature 0.5～2h again, and furnace cooling behind constant temperature 0.5～2h promptly gets the fluorenyl-containing polyimide that is used for high-temperature resistance adhesive; Wherein, above-mentioned building-up process is all carried out under the protection of inert nitrogen gas, argon gas or helium, and non-proton type polar solvent is selected from N, N '-N,N-DIMETHYLACETAMIDE, N, N '-N or N SL 1332.Other step and parameter are identical with embodiment seven.
In this embodiment 3,3 ', 4,4 '-to support adjacent pyromellitic dianhydride be that Beijing Bomi Sci. & Tech. Co., Ltd. produces to oxygen.
In this embodiment the fluorenyl polyamic acid that contains by step 1 to four preparation is carried out the infrared spectrum test, the result is as shown in Figure 1.Visible by Fig. 1, C=O stretching vibration absorption peak is at 1710cm among the-COOH
-1Near, C=O stretching vibration absorption peak 1660cm among the-CONH-
-1Near, 1550cm
-1Near what occur is C-N stretching vibration absorption peak, 1600cm
-1And 1500cm
-1Near what occur is phenyl ring skeletal vibration absorption peak, 3200cm
-1The place belong to-NH-in the N-H stretching vibration peak, 3050cm
-1And 2935cm
-1About occur be respectively-NH
2With N-H among the-COOH and-OH stretching vibration peak.Above absorption peak explanation has produced and has contained the fluorenyl polyamic acid.In this embodiment the fluorenyl-containing polyimide by step 1 to five preparation is carried out the infrared spectrum test, the result is as shown in Figure 2.Visible by Fig. 2, C=O asymmetrical stretching vibration absorption peak is at 1771cm in the imide ring
-1Near, C=O symmetrical stretching vibration absorption peak appears at 1718cm in the imide ring
-1Near, 1369cm
-1About what occur is the C-N stretching vibration absorption peak in the imide bond, 1077cm
-1Near be-the O-absorption peak 3055cm
-1Near occur be-NH
2In the N-H stretching vibration peak.Above description of step five has been accomplished the pass ring dehydration that contains the fluorenyl polyamic acid, has produced fluorenyl-containing polyimide.Ir spectra spectrogram (Fig. 1 and Fig. 2) before and after the contrast amidation is visible, contains the 3200cm of original secondary amine in the fluorenyl polyamic acid
-1Near absorption peak disappears, original 1660cm
-1And 1550cm
-1Near absorption peak disappears, and the substitute is 1369cm in the fluorenyl-containing polyimide
-1About C-N stretching vibration absorption peak in the imide bond that occurs.
Embodiment nine: this embodiment and embodiment eight are different be in the step 2 with step 1 obtain 9,9 '-two (4-aminophenyl) fluorenes and 4 added reactor drum in 3: 7 in molar ratio.Other step and parameter are identical with embodiment eight.
Embodiment ten: this embodiment and embodiment eight are different be in the step 2 with step 1 obtain 9,9 '-two (4-aminophenyl) fluorenes and 4 added reactor drum in 5: 5 in molar ratio.Other step and parameter are identical with embodiment eight.
Embodiment 11: this embodiment and embodiment eight are different be in the step 2 with step 1 obtain 9,9 '-two (4-aminophenyl) fluorenes and 4 added reactor drum in 9: 1 in molar ratio.Other step and parameter are identical with embodiment eight.
Embodiment 12: this embodiment and embodiment eight to 11 are different is in the step 3 in non-proton type polar solvent and the step 29; 9 '-ratio of two (4-aminophenyl) fluorenes and 4 mixture is 5L～6L: 1mol.Other step and parameter are identical with embodiment eight to 11.
Embodiment 13: this embodiment and embodiment eight to 12 are different is in the step 3 in non-proton type polar solvent and the step 29; 9 '-ratio of two (4-aminophenyl) fluorenes and 4 mixture is 5.2L～5.6L: 1mol.Other step and parameter are identical with embodiment eight to 12.
Embodiment 14: that this embodiment and embodiment eight to 13 are different is continuously stirring reaction 4h in the step 4.Other step and parameter are identical with embodiment eight to 13.
Embodiment 15: what this embodiment and embodiment eight to 14 were different is that twice constant temperature time is 1h in the step 5.Other step and parameter are identical with embodiment eight to 14.
Embodiment 16: this embodiment and embodiment eight to 15 are different is that temperature rise rate in the step 5 is 5-10 ℃/min.Other step and parameter are identical with embodiment eight to 15.
Embodiment 17: what this embodiment and embodiment eight to 16 were different is that used reaction vessel is a four-hole bottle in the building-up process.Other step and parameter and embodiment eight to ten six phases are together.
Embodiment 18: what this embodiment and embodiment eight were different is that fluorenyl-containing polyimide is through the following steps synthetic: one, 18g (0.1mol) Fluorenone, 75.2g (0.8mol) aniline and 5g methanesulfonic are joined in the 200ml four-hole bottle; Stirring also is warming up to 160 ℃, insulation reaction 10h.Leave standstill 14h after adding 50g ethanol and 5g triethylamine again, suction filtration then, again through re-crystallizing in ethyl acetate, after the vacuum-drying 9,9 '-two (4-aminophenyl) fluorenes (BAFL); Two, the 4 of 9,9 of the 0.075mol that step 1 is obtained (26.1g) '-two (4-aminophenyl) fluorenes and 0.175mol (35g) joins in the 2000ml four-hole bottle and mixes, and gets both mixtures; Three, the N that in the 2000ml four-hole bottle, adds 1300ml again, N '-N,N-DIMETHYLACETAMIDE, stirring and dissolving gets clear solution; Four, the 2000ml four-hole bottle is put into ice bath, treat that solution that step 3 obtains is cooled to 0 ℃ after, under whipped state, in solution, add 3 of 0.25mol; 3 ', 4,4 '-after oxygen supports adjacent pyromellitic dianhydride; Continue stirring reaction 3-5h again, obtain containing the polyamic acid of fluorenyl; Five, the polyamic acid that step 4 is obtained is put into baking oven and is warming up to 200 ℃, is warming up to 250 ℃ behind the constant temperature 1h again, and furnace cooling behind the constant temperature 1h promptly gets the fluorenyl-containing polyimide that is used for high-temperature resistance adhesive.Other step and parameter are identical with embodiment eight.
Embodiment 19: what this embodiment and embodiment eight were different is that fluorenyl-containing polyimide is through the following steps synthetic: one, 18g (0.1mol) Fluorenone, 75.2g (0.8mol) aniline and 5g methanesulfonic are joined in the 200ml four-hole bottle; Stirring also is warming up to 160 ℃, insulation reaction 10h.Leave standstill 14h after adding 50g ethanol and 5g triethylamine again, suction filtration then, again through re-crystallizing in ethyl acetate, after the vacuum-drying 9,9 '-two (4-aminophenyl) fluorenes (BAFL); Two, the 4 of 9,9 of the 0.125mol that step 1 is obtained (25g) '-two (4-aminophenyl) fluorenes and 0.125mol (4.35g) joins in the 2000ml four-hole bottle and mixes, and gets both mixtures; Three, in the 2000ml four-hole bottle, add the N SL 1332 of 1400ml again, stirring and dissolving gets clear solution; Four, the 2000ml four-hole bottle is put into ice bath, treat that solution that step 3 obtains is cooled to 0 ℃ after, under whipped state, in solution, add 3 of 0.25mol; 3 ', 4,4 '-after oxygen supports adjacent pyromellitic dianhydride; Continue stirring reaction 5h again, obtain containing the polyamic acid of fluorenyl; Five, the polyamic acid that step 4 is obtained is put into baking oven and is warming up to 200 ℃, is warming up to 250 ℃ behind the constant temperature 1h again, and furnace cooling behind the constant temperature 1h promptly gets the fluorenyl-containing polyimide that is used for high-temperature resistance adhesive.Other step and parameter are identical with embodiment eight.
Embodiment 20: what this embodiment and embodiment seven were different is that stablizer is triethylamine, tripropyl amine or diethylammonium methylamine.Other parameter is identical with embodiment seven.
Embodiment 21: what this embodiment and embodiment seven, 20 were different is that water-retaining agent is 4A molecular sieve or 100～300 order lime powders.Other parameter is identical with embodiment seven, 20.
Embodiment 22: what this embodiment and embodiment seven, 20 or 21 were different is before solubility fluorenyl-containing polyimide and N SL 1332 mixed dissolution, also adds the bismaleimides of pressing 1～5 part of ratio of quality and the number of copies.Other step and parameter are identical with embodiment seven, 20 or 21.
Bismaleimides is the commercially available prod in this embodiment.
Embodiment 23: what this embodiment and embodiment seven were different is that the preparation method who is used for the fluorenyl-containing polyimide of high-temperature resistance adhesive is: by ratio of quality and the number of copies the solubility fluorenyl-containing polyimide that 10～20 parts of embodiments 18 obtain is added 60～80 parts of N SL 1332 mixed dissolutions; Press ratio of quality and the number of copies again and add 1～5 part triethylamine stablizer and 5～10 parts 4A molecular sieve; Stir, promptly get fluorenyl-containing polyimide high temperature-resistant adhesive.Other step and parameter are identical with embodiment seven.
In this embodiment the fluorenyl-containing polyimide high temperature-resistant adhesive for preparing has been carried out thermal weight loss (TG) and analyzed and heat machinery (DMA) analysis, test result is seen Fig. 3 and Fig. 4 respectively.Can be known that by Fig. 3 the initial heat decomposition temperature of fluorenyl-containing polyimide high temperature-resistant adhesive is 470 ℃, temperature was 536 ℃ in weightless 5% o'clock, and weightless 10% o'clock temperature is 570 ℃.Can know that by Fig. 4 the second-order transition temperature of fluorenyl-containing polyimide high temperature-resistant adhesive is 294 ℃.The thermally-stabilised good of fluorenyl-containing polyimide high temperature-resistant adhesive that this embodiment obtains is described, can satisfies requirement as high temperature adhesive.
Table 1 is the fluorenyl-containing polyimide high temperature-resistant adhesive of embodiment 22 preparation be used to the to bond shearing resistance test result of carbon steel.
In this embodiment with the preparation fluorenyl-containing polyimide high temperature-resistant adhesive bonded carbon steel construction piece; The back carbon steel structure spare that will bond is put into heat treatment furnace dry 1h under 120 ℃; Be warming up to 250 ℃ of after fixing 1h then, again through 370 ℃ of heat treated 1h, last furnace cooling; Then the back carbon steel structure spare that bonds is carried out the shearing resistance test, test result is seen table 1.
Table 1
| Probe temperature | 25 |
300 |
350 |
400℃ |
| Shearing resistance (MPa) | 14 | 12.6 | 10 | 6.5 |
Visible by table 1, the high temperature cohesive strength of the fluorenyl-containing polyimide high temperature-resistant adhesive that this embodiment obtains is high, can be used for the bonding of structural part.The shearing resistance of 25 ℃ of carbon steels that bond down is 14MPa, and the shearing resistance of 400 ℃ of carbon steels that bond down still reaches 6.5MPa, can satisfy structural part agglutinating cohesive strength requirement under 400 ℃ of conditions.
Embodiment 24: what this embodiment and embodiment seven were different is that the preparation method who is used for the fluorenyl-containing polyimide of anti-high-temperature resistance adhesive is: by ratio of quality and the number of copies solubility fluorenyl-containing polyimide and 1～5 part of bismaleimides that 10～20 parts of embodiments 19 obtain added 60～80 parts of N SL 1332 mixed dissolutions; Press ratio of quality and the number of copies again and add 1～5 part triethylamine stablizer and 5～10 parts lime powder; Stir, promptly get fluorenyl-containing polyimide high temperature-resistant adhesive.Other step and parameter are identical with embodiment seven.
In this embodiment the fluorenyl-containing polyimide high temperature-resistant adhesive for preparing has been carried out thermal weight loss (TG) and analyzed and heat machinery (DMA) analysis, test result is seen Fig. 5 and Fig. 6 respectively.Can be known that by Fig. 5 the initial heat decomposition temperature of fluorenyl-containing polyimide high temperature-resistant adhesive is 450 ℃, temperature was 484 ℃ in weightless 5% o'clock, and weightless 10% o'clock temperature is 511 ℃.Can know that by Fig. 6 the second-order transition temperature of fluorenyl-containing polyimide high temperature-resistant adhesive is 310 ℃.The thermally-stabilised good of fluorenyl-containing polyimide high temperature-resistant adhesive that this embodiment obtains is described, can satisfies requirement as high temperature adhesive.
Table 2 is the fluorenyl-containing polyimide high temperature-resistant adhesive of embodiment 23 preparation be used to bond shearing resistance test results of carbon steel.
In this embodiment with the preparation fluorenyl-containing polyimide high temperature-resistant adhesive bonded carbon steel construction piece; The back carbon steel structure spare that will bond is put into heat treatment furnace dry 1h under 120 ℃; Be warming up to 250 ℃ of after fixing 1h then, again through 370 ℃ of heat treated 1h, last furnace cooling; Then the back carbon steel structure spare that bonds is carried out the shearing resistance test, test result is seen table 2.
Table 2
| Probe temperature | 25 |
300 |
350 |
400℃ |
| Shearing resistance (MPa) | 13.2 | 10.7 | 9.8 | 6.7 |
Visible by table 2, the high temperature cohesive strength of the fluorenyl-containing polyimide high temperature-resistant adhesive that this embodiment obtains is high, can be used for the bonding of structural part.25 ℃ down the shearing resistances of bonding carbon steels be 13.2MPa, under the high temperature, especially under 400 ℃, the shearing resistance of bonding carbon steel reaches 6.7MPa, can satisfy structural part agglutinating cohesive strength requirement under 400 ℃ of conditions.
Claims (9)
1. fluorenyl-containing polyimide high temperature-resistant adhesive; It is characterized in that fluorenyl-containing polyimide high temperature-resistant adhesive mainly processed by 10～20 parts of solubility fluorenyl-containing polyimides, 60～80 parts of N SL 1332s, 1～5 part of tertiary amines stablizer and 5～10 parts of water-retaining agents by ratio of quality and the number of copies, the structural formula of said fluorenyl-containing polyimide is:
Wherein, m, n are the unitary mole number of repeating structure, m: n=(1/9～9): 1, and its weight-average molecular weight is 80000～150000.
2. a kind of fluorenyl-containing polyimide high temperature-resistant adhesive according to claim 1 is characterized in that stablizer is triethylamine, tripropyl amine or diethylammonium methylamine.
3. a kind of fluorenyl-containing polyimide high temperature-resistant adhesive according to claim 2 is characterized in that water-retaining agent is 4A molecular sieve or 100～300 order lime powders.
4. according to claim 1 or 3 described a kind of fluorenyl-containing polyimide high temperature-resistant adhesives, it is characterized in that fluorenyl-containing polyimide high temperature-resistant adhesive also comprises 1～5 part of bismaleimides by ratio of quality and the number of copies.
5. the preparation method of fluorenyl-containing polyimide high temperature-resistant adhesive as claimed in claim 1; It is characterized in that the preparation method is: take by weighing 10～20 parts of solubility fluorenyl-containing polyimides, 60～80 parts of N SL 1332s, 1～5 part of tertiary amines stablizer and 5～10 parts of water-retaining agents respectively by ratio of quality and the number of copies; Then the solubility fluorenyl-containing polyimide is added mixed dissolution in the N SL 1332; Add tertiary amines stablizer and water-retaining agent again; Stir, promptly get fluorenyl-containing polyimide high temperature-resistant adhesive.
6. the preparation method of fluorenyl-containing polyimide high temperature-resistant adhesive according to claim 5 is characterized in that the structural formula of described fluorenyl-containing polyimide is:
7. the preparation method of fluorenyl-containing polyimide high temperature-resistant adhesive according to claim 5 is characterized in that stablizer is triethylamine, tripropyl amine or diethylammonium methylamine.
8. according to the preparation method of claim 5 or 7 described fluorenyl-containing polyimide high temperature-resistant adhesives, it is characterized in that water-retaining agent is 4A molecular sieve, 100～300 order lime powders.
9. the preparation method of fluorenyl-containing polyimide high temperature-resistant adhesive according to claim 8 is characterized in that before fluorenyl-containing polyimide adds N SL 1332 mixed dissolution, also pressing the bismaleimides that ratio of quality and the number of copies adds 1～5 part.
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|---|---|---|---|---|
| CN1385487A (en) * | 2002-05-25 | 2002-12-18 | 中国科学院兰州化学物理研究所 | Polyimide base high temp.-resistant and radiation-resistant lubricating paint |
| CN1445324A (en) * | 2003-04-11 | 2003-10-01 | 上海华谊（集团）公司 | Method for preparing high-temp. resistant adhesive |
| EP2048209A1 (en) * | 2006-08-04 | 2009-04-15 | Hitachi Chemical Company, Ltd. | Adhesive composition, and connection structure for circuit member |
-
2009
- 2009-06-17 CN CN2009100723141A patent/CN101580687B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385487A (en) * | 2002-05-25 | 2002-12-18 | 中国科学院兰州化学物理研究所 | Polyimide base high temp.-resistant and radiation-resistant lubricating paint |
| CN1445324A (en) * | 2003-04-11 | 2003-10-01 | 上海华谊（集团）公司 | Method for preparing high-temp. resistant adhesive |
| EP2048209A1 (en) * | 2006-08-04 | 2009-04-15 | Hitachi Chemical Company, Ltd. | Adhesive composition, and connection structure for circuit member |
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| CN101580687A (en) | 2009-11-18 |
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