Quick responsive, shape memory thermoset polyimide and preparation method thereof

Abstract

A fast-response thermoplastic shape-memory polyimide and a preparation method thereof, related to a polyimide and a preparation method thereof. The present invention aims to solve the problem in high-temperature conditions of slow shape recovery poor stability, and poor mechanical properties of a shape-memory polymer prepared by utilizing an existing method. The structural formula of the polyamide of the present invention is as represented by formula (I). The preparation method is: 1. preparation of a diamine solution; 2. preparation of an anhydride-terminated high molecular weight polyamic acid; 3. preparation of a viscous sol-gel; and, 4. preparation of the thermoplastic shape-memory polyimide. The thermoplastic shape-memory polyimide prepared per the present invention is provided with a very fast shape recovery rate and improved shape-memory effect. The present invention is applicable in the field of polyimide preparation.

Claims

1. A method for preparing a quick responsive, high-performance, thermoset shape memory polyimide, having the following steps of: I. preparation of a diamine solution: weighting out 1,3-bis(3-aminophenoxy)benzene monomer and charging it into a three-neck flask containing N,N-dimethylacetamide solvent, then stirring the contents in the flask under the protection of dry nitrogen at room temperature until the 1,3-bis-(3-aminophenoxy)benzene monomer is completely dissolved, so as to obtain a diamine solution; wherein the molar ratio by volume between N,N-dimethylacetamide solvent and 1,3-bis(3-aminophenoxy)benzene monomer is 1 mL: (0.2-0.33) mmoL; II. preparation of an anhydride-terminated high molecular weight polyamic acid: adding bis-phenol A type diether-dianhydride monomer for 4-6 times to the diamine solution obtained in step I, then stirring the resultant for 16-20 hours at a speed of 200-300 r/min at room temperature to obtain the anhydride-terminated high molecular weight polyamic acid; wherein the amount of each addition of the bisphenol A type diether dianhydride monomer is equal to or less than half of the amount of prior addition; wherein the mass ratio of the bisphenol A type diether dianhydride monomer as described in step II to 1,3-bis(3-aminophenoxy)benzene monomer in the diamine solution is 1: (0.85-0.97); III. preparation of a viscous sol-gel adding tri(4-aminophenyl)amine to the anhydride-terminated high molecular weight polyamic acid obtained in step II, and then stirring the resultant for 5-7 hours at a speed of 260-350 r/min at room temperature to obtain a sol-gel, and drying the obtained sol-gel at 40-65 C. in a vacuum oven for 0.5-2 hours to obtain a viscous sol-gel; and the mass ratio of the tri(4-aminophenyl)amine as described in step III to the bisphenol A type diether dianhydride monomer in the anhydride-terminated high molecular weight polyamic acid is (0.02-0.10):1; IV. preparation of a thermoset shape memory polyimide pouring the viscous sol-gel obtained in step III on a substrate, heating the resultant from room temperature to 70-90 C. at a heating rate of 1-2 C./min, and keeping it at the temperature for 1-2 hours; then heating the resultant to 120-140 C. at a heating rate of 1-2 C./min, and keeping it at the temperature for 1-2 hours; then heating the resultant to 170-190 C. at a heating rate of 1-2 C./min, and keeping it at the temperature for 1-2 hours; then heating the resultant to 220-250 C. at a heating rate of 1-3 C./min, and keeping it at the temperature for 1-2 hours; then heating the resultant to 270-290 C. at a heating rate of 1-3 C./min, and keeping it at the temperature for 1-2 hours; and finally, cooling the resultant at a cooling rate of 1-3 C./min to room temperature; immersing the substrate that has already been cooled down to room temperature in distilled water to peel off a solid film, then washing the solid film for 3-5 times with distilled water and finally heating it at a temperature condition of 120-180 C. for 360-600 minutes to produce the thermoset shape memory polyimide.

2. The method for preparing a quick responsive, high-performance, thermoset shape memory polyimide according to claim 1, wherein the purity of the 1,3-bis(3-aminophenoxy)benzene monomer in step I is 98%.

3. The method for preparing a quick responsive, high-performance, thermoset shape memory polyimide according to claim 1, wherein in step II, the purity of the bisphenol A type diether dianhydride monomer is 97%.

4. The method for preparing a quick responsive, high-performance, thermoset shape memory polyimide according to claim 1, wherein the purity of the tri(4-aminophenyl)amine is >98%.

5. The method for preparing a quick responsive, high-performance, thermoset shape memory polyimide according to claim 1, wherein in step I, the molar ratio by volume between N,N-dimethylacetamide solvent and 1,3-bis(3-aminophenoxy) benzene monomer is 1 mL: 0.25 mmoL.

6. The method for preparing a quick responsive, high-performance, thermoset shape memory polyimide according to claim 1, wherein in step II, the mass ratio of the bisphenol A type diether dianhydride monomer to 1,3-bis(3-aminophenoxy) benzene monomer in the diamine solution is 1:(0.90-0.95).

7. The method for preparing a quick responsive, high-performance, thermoset shape memory polyimide according to claim 1, wherein in step III, the mass ratio of the tri(aminophenyl)amine to the bisphenol A type diether dianhydride monomer in the anhydride terminated high molecular weight polyamic acid is (0.05-0.08):1.

8. The method for preparing a quick responsive, high-performance, thermoset shape memory polyimide according to claim 1, wherein in step IV, heating the resultant from room temperature to 80-90 C. at a heating rate of 1-2 C./min, and keeping it at the temperature for 1-2 hours; then heating the resultant to 130-140 C. at a heating rate of 1-2 C./min, and keeping it at the temperature for 1-2 hours; then heating the resultant to 180-190 C. at a heating rate of 1-2 C./min, and keeping it at the temperature for 1-2 hours; then heating the resultant to 240-250 C. at a heating rate of 1-3 C./min, and keeping it at the temperature for 1-2 hours; then heating the resultant to 280-290 C. at a heating rate of 1-3 C./min, and keeping it at the temperature for 1-2 hours; and finally keeping it the resultant at a cooling rate of 1-3 C./min to room temperature.

9. The method for preparing a quick responsive, high-performance, thermoset shape memory polyimide according to claim 1, wherein in step IV, the heating at a temperature of 150-180 C. is conducted for 450-600 minutes.

Description

DESCRIPTION OF THE FIGURES

(1) FIG. 1 shows a schematic network structure of the quick responsive, thermoset, shape memory polyimides prepared according to the present invention, wherein, the curved line represents the chain segments of polyimide molecules, and the dots represent triamine crosslinker;

(2) FIG. 2 shows the structure of the chain segments between the crosslinking points of the quick responsive, thermoset, shape memory polyimides prepared according to the present invention;

(3) FIG. 3 shows an IR spectrum of the quick responsive, thermoset, shape memory polyimides prepared according to Example 1;

(4) FIG. 4 shows a graph of the loss factor of the quick responsive, thermoset, shape memory polyimides prepared according to Example 1;

(5) FIG. 5 shows a graph of the storage modulus of the quick responsive, thermoset, shape memory polyimides prepared according to Example 1;

(6) FIG. 6 shows a TGA graph of the quick responsive, thermoset, shape memory polyimides prepared according to Example 1;

(7) FIG. 7 shows a picture of the quick responsive, thermoset, shape memory polyimides in flat panel form prepared according to Example 1 and positioned on a hot stage, which was bended at elevated temperature and fixed at room temperature to yield a temporary shape;

(8) FIG. 8 is a picture showing the shape recovery of the quick responsive, thermoset, shape memory polyimides prepared according to Example 1 after 1 second on the hot stage of 210 C.;

(9) FIG. 9 is a picture showing the shape recovery of the quick responsive, thermoset, shape memory polyimides prepared according to Example 1 after 2 seconds on the hot stage of 210 C.;

(10) FIG. 10 is a picture showing the recovery to the original shape of the quick responsive, thermoset, shape memory polyimides prepared according to Example 1 after 3 seconds on the hot stage of 210 C.

EXAMPLES

Example 1

(11) A quick responsive, high-performance thermoset, shape memory polyimide according to the example, had a structure of:

(12) ##STR00002##

(13) wherein, n was 58-156, the said quick responsive, high-performance thermoset, shape memory polyimide had a molecular weight of 46-124 k.

(14) The example used 1,3-bis(3-aminophenoxy)benzene and bisphenol A type diether dianhydride as the reaction monomers to prepare an anhydride terminated polyamic acid precursor, which then formed a network structure by using triamine(4-aminophenyl) to crosslink the polyamic acid, and the resultant was subject to a gradient heating procedure to provide a thermoset shape memory polyimide.

Example 2

(15) This example was almost the same as Example 1, except that n was 80-156, and the quick responsive, high-performance thermoset, shape memory polyimide had a molecular weight of 80-124 k.

Example 3

(16) This example was almost the same as Example 1 or 2, except that n was 100-156, and the quick responsive, high-performance thermoset, shape memory polyimide had a molecular weight of 100-124 k.

Example 4

(17) The preparation method of a quick responsive, high-performance, thermosetting, shape memory polyimide according to this example was achieved by the following steps:

(18) I. Preparation of a Diamine Solution

(19) 1,3-bis(3-aminophenoxy)benzene monomer was weighted out and charged into a three-neck flask containing N,N-dimethylacetamide solvent, and then stirred under the protection of dry nitrogen at room temperature until 1,3-bis(3-aminophenoxy)benzene monomer was completely dissolved, so as to provide a diamine solution;

(20) wherein the molar ratio by volume between N,N-dimethylacetamide solvent and 1,3-bis(3-aminophenoxy)benzene monomer was 1 mL:(0.2-0.33) mmoL;

(21) II. Preparation of Anhydride-Terminated High Molecular Weight Polyamic Acid

(22) Bisphenol A type diether dianhydride monomer was added for 4-6 times to the diamine solution obtained in step I, the resultant was stirred for 16-20 hours at a speed of 200-300 r/min at room temperature to obtain an anhydride-terminated high molecular weight polyamic acid; wherein, the amount of each addition of the bisphenol A type diether dianhydride monomer is equal to or less than half of the amount of prior addition;

(23) wherein, the mass ratio of the bisphenol A type diether dianhydride monomer as mentioned in step II to 1,3-bis(3-aminophenoxy)benzene in the diamine solution was 1:(0.85-0.97);

(24) III. Preparation of a Viscous Sol-Gel

(25) Tri(4-aminophenyl)amine was added to the anhydride-terminated high molecular weight polyamic acid obtained in step II, the resultant was stirred for 5-7 hours at a speed of 260-350 r/min at room temperature to produce a sol-gel. Then the obtained sol-gel was dried at 40-65 C. in a vacuum oven for 0.5-2 hours to yield a viscous sol-gel;

(26) the mass ratio of the tri(4-aminophenyl)amine mentioned in step III to bisphenol A type diether dianhydride monomer in the anhydride-terminated high molecular weight polyamic acid was (0.02-0.10):1;

(27) IV. Preparation of Thermoset, Shape Memory Polyimides

(28) The viscous sol-gel obtained in step III was poured onto a substrate, then was heated from room temperature at a heating rate of 1-2 C./min to 70-90 C., and kept at the temperature for 1-2 hours; then was heated at a heating rate of 1-2 C./min to 120-140 C., and kept at the temperature for 1-2 hours; then was heated at a heating rate of 1-2 C./min to 170-190 C., and kept at the temperature for 1-2 hours; then was heated at a heating rate of 1-3 C./min to 220-250 C., and kept at the temperature for 1-2 hours; then was heated at a heating rate of 1-3 C./min to 270-290 C., and kept at the temperature for 1-2 hours;

(29) finally, it was cooled at a rate of 1-3 C./min to room temperature; the substrate that has already been cooled down to room temperature was immersed in distilled water to peel off a solid film, which was then washed for 3-5 times using distilled water and finally heated at 120-180 C. for 360-600 minutes to produce thermoset, shape memory polyimides.

(30) The N,N-dimethylacetamide mentioned in Example 1 was commercial available and of analytical pure grade, and was vacuum distilled after the removal of water.

(31) The tri(4-aminophenyl)amine in Example 3 comprised three amino-functional group, rendering the total number of amino functional groups of tri(4-aminophenyl)amine and diamine being equal to the total number of anhydride functional groups of dianhydride monomer, and the mass ratio of the dianhydride to tri(4-aminophenyl)amine was 1:0.02-1:0.10.

(32) The present example used 1,3-bis(3-aminophenoxy)benzene and bisphenol A type diether dianhydride as the reaction monomers to prepare anhydride terminated polyamic acid precursor, which was then crosslinked to form a network structure by using triamine(4-aminophenyl), and further subject to a gradient heating procedure to provide thermoset shape memory polyimide.

(33) The reaction scheme of the step II according to the example was as follows:

(34) ##STR00003##

(35) The reaction scheme of the step IV according to this example was as follows:

(36) ##STR00004##

Example 5

(37) This example was almost the same as Example 4, except that the purity of 1,3-bis(3-aminophenoxy)benzene monomer as mentioned in step I was 98%.

Example 6

(38) This example was almost the same as Examples 4 or 5, except that the purity of the bisphenol A type diether dianhydride monomer as mentioned in step II was 97%.

Example 7

(39) This example was almost the same as one of the Examples 4-6, except that the purity of tri(4-aminophenyl)amine as mentioned in step III was >98%.

Example 8

(40) This example was almost the same as one of the Examples 4-7, except that the molar ratio by volume between N,N-dimethylacetamide solvent and 1,3-bis(3-aminophenoxy) benzene monomer as mentioned in step I was 1 mL:0.27-0.32 mmoL.

Example 9

(41) This example was almost the same as one of the Examples 4-8, except that the molar ratio by volume between N,N-dimethylacetamide solvent and 1,3-bis(3-aminophenoxy) benzene monomer as mentioned in step I was 1 mL: 0.33 mmoL.

Example 10

(42) This example was almost the same as one of the Examples 4-9, except that the mass ratio of bisphenol A type diether dianhydride monomer to 1,3-bis(3-aminophenoxy)benzene monomer in the diamine solution as mentioned in step II was 1:(0.90-0.95).

Example 11

(43) This example was almost the same as one of the Examples 4-10, except that the mass ratio of bisphenol A type diether dianhydride monomer to 1,3-bis(3-aminophenoxy)benzene monomer in the diamine solution as mentioned in step II was 1: (O. 90-0.92).

Example 12

(44) This example was almost the same as one of the Examples 4-11, except that the mass ratio of bisphenol A type diether dianhydride monomer to 1,3-bis(3-aminophenoxy)benzene monomer in the diamine solution as mentioned in step II was 1:0.91.

Example 13

(45) This example was almost the same as one of the Examples 4-12, except that the mass ratio of tri(aminophenyl)amine to bisphenol A type diether dianhydride monomer in the anhydride terminated high molecular weight polyamic acid as mentioned in step III was (0.03-0.09):1.

Example 14

(46) This example was almost the same as one of the Examples 4-13, except that the mass ratio of tri(aminophenyl)amine to bisphenol A type diether dianhydride monomer in the anhydride terminated high molecular weight polyamic acid as mentioned in step III was (0.04-0.08):1.

Example 15

(47) This example was almost the same as one of the Examples 4-14, except that the mass ratio of tri(aminophenyl)amine to bisphenol A type diether dianhydride monomer in the anhydride terminated high molecular weight polyamic acid as mentioned in step III was (0.05-0.07):1.

Example 16

(48) This example was almost the same as one of the Examples 4-15, except that the mass ratio of tri(aminophenyl)amine to bisphenol A type diether dianhydride monomer in the anhydride terminated high molecular weight polyamic acid as mentioned in step III was 0.06:1.

Example 17

(49) This example was almost the same as one of the Examples 4-16, except that the stirring as mentioned in step II was at a rate of 250-300 r/min and lasted for 18-20 hours.

Example 18

(50) This example was almost the same as one of the Examples 4-17, except that the stirring as mentioned in step II was at a rate of 280-300 r/min and lasted for 19-20 hours.

Example 19

(51) This example was almost the same as one of the Examples 4-18, except that the stirring as mentioned in step III was at a rate of 280-350 r/min and lasted for 5-7 hours.

Example 20

(52) This example was almost the same as one of the Examples 4-19, except that the stirring as mentioned in step III was at a rate of 300-350 r/min and lasted for lasted 6-7 hours.

Example 21

(53) This example was almost the same as one of the Examples 4-20, except that the stirring as mentioned in step III was at a rate of 320-350 r/min and lasted for 6-7 hours.

Example 22

(54) This example was almost the same as one of the Examples 4-21, except that the stirring as mentioned in step III was at a rate of 320-350 r/min and lasted for 6-7 hours.

Example 23

(55) This example was almost the same as one of the Examples 4-22, except that the sol-gel obtained in step III was dried in a vacuum oven at a temperature of 45-65 C. for 0.8-2 hours.

Example 24

(56) This example was almost the same as one of the Examples 4-23, except that the sol-gel obtained in step III was dried in a vacuum oven at a temperature of 50-65 C. for 1-2 hours.

Example 25

(57) This example was almost the same as one of the Examples 4-24, except that the sol-gel obtained in step III was dried in a vacuum oven at a temperature of 55-65 C. for 1.5-2 hours.

Example 26

(58) This example was almost the same as one of the Examples 4-25, except that the sol-gel obtained in step III was dried in a vacuum oven at a temperature of 60-65 C. for 1.5-2 hours.

Example 27

(59) This example was almost the same as one of the Examples 4-26, except that the sol-gel obtained in step III was dried in a vacuum oven at a temperature of 60-65 C. for 1.8-2 hours.

Example 28

(60) This example was almost the same as one of the Examples 4-27, except that, in step IV,

(61) the resultant was heated from room temperature at a rate of 1-2 C./min to 75-90 C., and was kept at the temperature for 1-2 hours;

(62) then the resultant was heated at a rate of 1-2 C./min to 125-140 C., and was kept at the temperature for 1-2 hours;

(63) then the resultant was heated at a rate of 1-2 C./min to 175-190 C., and was kept at the temperature for 1-2 hours;

(64) then the resultant was heated at a rate of 1-3 C./min to 230-250 C., and was kept at the temperature for 1-2 hours;

(65) then the resultant was heated at a rate of 1-3 C./min to 275-290 C., and was kept at the temperature for 1-2 hours;

(66) finally, the resultant was cooled at a rate of 1-3 C./min to room temperature.

Example 29

(67) This example was almost the same as one of the Examples 4-28, except that, in step IV,

(68) the resultant was heated from room temperature at a rate of 1-2 C./min to 80-90 C., and was kept at the temperature for 1-2 hours;

(69) then the resultant was heated at a rate of 1-2 C./min to 130-140 C., and was kept at the temperature for 1-2 hours;

(70) then the resultant was heated at a rate of 1-2 C./min to 180-190 C., and was kept at the temperature for 1-2 hours;

(71) then the resultant was heated at a rate of 1-3 C./min to 235-250 C., and was kept at the temperature for 1-2 hours;

(72) then the resultant was heated at a rate of 1-3 C./min to 280-290 C., and was kept at the temperature for 1-2 hours;

(73) finally the resultant was cooled at a rate of 1-3 C./min to room temperature.

Example 30

(74) This example was almost the same as one of the Examples 4-29, except that, in step IV,

(75) the resultant was heated from room temperature at a rate of 1-2 C./min to 85-90 C., and was kept at the temperature for 1.5-2 hours;

(76) then the resultant was heated at a rate of 1-2 C./min to 135-140 C., and was kept at the temperature for 1.5-2 hours;

(77) then the resultant was heated at a rate of 1-2 C./min to 185-190 C., and was kept at the temperature for 1.5-2 hours;

(78) then the resultant was heated at a rate of 1-3 C./min to 240-250 C., and was kept at the temperature for 1.5-2 hours;

(79) then the resultant was heated at a rate of 1-3 C./min to 285-290 C., and was kept at the temperature for 1.5-2 hours;

(80) finally the resultant was cooled at a rate of 1-3 C./min to room temperature.

Example 31

(81) This example was almost the same as one of the Examples 4-30, except that, in step IV, the heating was performed at a temperature of 130-180 C. for 380-600 minutes.

Example 32

(82) This example was almost the same as one of the Examples 4-31, except that, in step IV, the heating was performed at a temperature of 140-180 C. for 400-600 minutes.

Example 33

(83) This example was almost the same as one of the Examples 4-32, except that, in step IV, the heating was performed at a temperature of 150-180 C. for 450-600 minutes.

Example 34

(84) This example was almost the same as one of the Examples 4-33, except that, in step IV, the heating was performed at a temperature of 155-180 C. for 480-600 minutes.

Example 35

(85) This example was almost the same as one of the Examples 4-34, except that, in step IV, the heating was performed at a temperature of 160-180 C. for 500-600 minutes.

Example 36

(86) This example was almost the same as one of the Examples 4-35, except that, in step IV, the heating was performed at a temperature of 165-180 C. for 520-600 minutes.

Example 37

(87) This example was almost the same as one of the Examples 4-36, except that, in step IV, the heating was performed at a temperature of 170-180 C. for 550-600 minutes.

Example 38

(88) This example was almost the same as one of the Examples 4-37, except that, in step IV, the heating was performed at a temperature of 175-180 C. for 580-600 minutes.