CN105860071B - A kind of high temperature resistance and long service life shape memory polyimides and preparation method thereof - Google Patents
A kind of high temperature resistance and long service life shape memory polyimides and preparation method thereof Download PDFInfo
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- CN105860071B CN105860071B CN201610251907.4A CN201610251907A CN105860071B CN 105860071 B CN105860071 B CN 105860071B CN 201610251907 A CN201610251907 A CN 201610251907A CN 105860071 B CN105860071 B CN 105860071B
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 112
- 229920001721 polyimide Polymers 0.000 title claims abstract description 112
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000004985 diamines Chemical class 0.000 claims abstract description 22
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 19
- 238000007789 sealing Methods 0.000 claims abstract description 19
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 18
- 229920002521 macromolecule Polymers 0.000 claims abstract description 17
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 52
- 238000010438 heat treatment Methods 0.000 claims description 51
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 50
- 238000010792 warming Methods 0.000 claims description 40
- 239000011521 glass Substances 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 29
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 26
- 235000010290 biphenyl Nutrition 0.000 claims description 26
- 239000004305 biphenyl Substances 0.000 claims description 26
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 23
- 150000001412 amines Chemical class 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 22
- 239000012153 distilled water Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 239000002798 polar solvent Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 5
- 150000002466 imines Chemical class 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 description 14
- 230000003446 memory effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920000431 shape-memory polymer Polymers 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 3
- 239000012781 shape memory material Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000007334 memory performance Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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Abstract
A kind of high temperature resistance and long service life shape memory polyimides and preparation method thereof, it is related to a kind of polyimides and preparation method thereof.The purpose of the present invention is to solve there is no T at presentgThe problem of access times more than 230 DEG C are more than thousands of long-life shape memory polyimides.A kind of structural formula of high temperature resistance and long service life shape memory polyimides is：Preparation method：One, diamine solution is prepared；Two, the macromolecule polyamic acid of acid anhydride sealing end is prepared；Three, the thick collosol and gel of bubble-free is prepared；Four, gradient increased temperature obtains high temperature resistance and long service life shape memory polyimides.The present invention can get a kind of high temperature resistance and long service life shape memory polyimides.
Description
Technical field
The present invention relates to a kind of polyimides and preparation method thereof.
Background technology
Shape-memory material refers to that under certain condition after deformation and fixation, can perceive and ring with original shape
It answers the extraneous stimulation changed and restores the intellectual material of its original state.Marmem (SMA) and shape-memory polymer
(SMP) it is common shape-memory material, wherein SMA has been widely used for the numerous areas such as satellite antenna.Relative to SMA compared with
Small reversible strain facies ratio (being generally less than 8%), SMP is not only with >=100% reversible strain, the also low, processing with density
The advantages that being easy with recovery of shape temperature convenient for control, plays in numerous areas such as intelligent weaving, biologic medical, aerospaces
Increasingly important role.The excellent properties of shape memory effect and polyimides are combined by shape memory polyimides,
Flexible optoelectronic part and high-temperature shape-memory structure such as space deployable structure, intelligent jet engine, pyrostat and
The fields such as high temperature driven device have wide application prospects.
Cycle life is an important indicator of shape-memory material, and so-called cycle life refers to that material keeps high shape
The cycle-index of memory performance.The cycle life of normally shape memorial alloy such as NiTi alloys is between 100~100,000 times, specifically
Service life depends on experiment condition.And biologic medical is only used with SMP and is not repeated to use, common SMP its cycle life tests
Generally 3 times~5 times.And for needing the device repeatedly recycled, such as space structure, cycle life to be very important ginseng
Examine factor.However there is no shape memory polyimides access times at present is more than thousands of reports.
The present invention prepares a kind of novel long-life shape memory polyimides, is still kept when recycling for 1000 times or more
Excellent shape-memory properties.
Invention content
The purpose of the present invention is to solve there is no T at presentgAccess times more than 230 DEG C are more than thousands of long-lives
The problem of shape memory polyimides, and a kind of high temperature resistance and long service life shape memory polyimides is provided and preparation method thereof.
A kind of structural formula of high temperature resistance and long service life shape memory polyimides is：
Wherein, the value range of the n is 15~27.
A kind of preparation method of high temperature resistance and long service life shape memory polyimides, is completed according to the following steps：
One, by 4,4'- bis- (4- amino-benzene oxygens), biphenyl is added in aprotic polar solvent, then is stirred in a nitrogen atmosphere
It mixes to 4,4'- bis- (4- amino-benzene oxygens) biphenyl and is completely dissolved, obtain diamine solution；
The body of the amount and aprotic polar solvent of the substance of 4,4'- bis- (4- amino-benzene oxygens) biphenyl described in step 1
Product is than being (0.18mmoL~0.3mmoL):1mL；
Two, Bisphenol A Type Diether Dianhydride monomer is divided 4 times~6 times and is added in the diamine solution obtained in step 1, then
Room temperature and mixing speed are stirred to react 15h~30h under conditions of being 250r/min~550r/min, obtain the macromolecular of acid anhydride sealing end
Measure polyamic acid；
(4- amino-benzene oxygens) biphenyl of 4,4'- bis- and Bisphenol A Type Diether Dianhydride list in diamine solution described in step 2
The amount ratio of the substance of body is (0.85~1):1；
Three, three (4- aminophenyls) amine are added in the macromolecule polyamic acid of the acid anhydride sealing end obtained in step 2,
It is again 250r/min~550r/min in room temperature and mixing speed, is stirred to react 3h~7h, obtains collosol and gel；It will obtain again
Collosol and gel dry 1h~2h in the vacuum drying chamber that temperature is 50~70 DEG C, obtains the thick collosol and gel of bubble-free；
The amount of three (4- aminophenyls) amine and the substance of Bisphenol A Type Diether Dianhydride monomer in step 2 described in step 3
Than for (2~9):100；
Four, the thick collosol and gel of the bubble-free obtained in step 3 is coated uniformly on clean glass plate, then
It is started to warm up from room temperature to 80 DEG C~100 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min, and is 80 DEG C~100 DEG C in temperature
Lower heat preservation 1h~2h；
130 DEG C~150 DEG C are warming up to from 80 DEG C~100 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and in temperature
Degree is that 1h~2h is kept the temperature at 130 DEG C~150 DEG C；
180 DEG C~200 DEG C are warming up to from 130 DEG C~150 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and in temperature
Degree is that 1h~2h is kept the temperature at 180 DEG C~200 DEG C；
230 DEG C~250 DEG C are warming up to from 180 DEG C~200 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and in temperature
Degree is that 1h~2h is kept the temperature at 230 DEG C~250 DEG C；
280 DEG C~290 DEG C are warming up to from 230 DEG C~250 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and in temperature
Degree is that 1h~2h is kept the temperature at 280 DEG C~290 DEG C；
Room temperature is finally cooled to from 280 DEG C~290 DEG C with the rate of temperature fall of 1 DEG C/min~2 DEG C/min；
The glass plate that will drop to room temperature again is immersed in the solid film on glass plate is made to fall off in distilled water, then uses distilled water
Obtained solid film is rinsed well, finally by the solid film rinsed well under conditions of temperature is 100 DEG C~180 DEG C
300min~400min is heated, high temperature resistance and long service life shape memory polyimides is obtained.
The present invention includes following advantageous effect：
One, the T of high temperature resistance and long service life shape memory polyimides prepared by the present inventiongIt is 230 DEG C~236 DEG C, ensure that
Its shape memory effect can be applied to high-temperature field；
Two, high temperature resistance and long service life shape memory polyimides prepared by the present invention has excellent shape memory effect, and
And have the very long service life, after cycle more than 1000 times, still keep good shape fixed rate and shape recovery rate；
Three, high temperature resistance and long service life shape memory polyimides prepared by the present invention has excellent thermodynamic property, normal
Storage modulus when warm 60 DEG C of glassy states is 2.1GPa-2.6GPa；High temperature (Tg+ 20 DEG C) rubbery state when storage modulus be about
6.5MPa~7.3MPa after multiplicating, still keeps excellent thermodynamic property；
Four, the decomposition temperature when mass loss of high temperature resistance and long service life shape memory polyimides prepared by the present invention is 5%
Degree is 501 DEG C~505 DEG C, and the residual at 800 DEG C is 55.9%~57.3%, illustrates the high temperature resistance and long service life prepared by the present invention
Shape memory polyimides has excellent heat resistance.
Description of the drawings
Fig. 1 is the infrared spectrogram of high temperature resistance and long service life shape memory polyimides prepared by embodiment one；
Fig. 2 is the fissipation factor figure of high temperature resistance and long service life shape memory polyimides prepared by embodiment one；
Fig. 3 is the storage modulus figure of high temperature resistance and long service life shape memory polyimides prepared by embodiment one；
Fig. 4 is the hot weightless picture of high temperature resistance and long service life shape memory polyimides prepared by embodiment one；
Fig. 5 is the temporary shapes figure of the 1st cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Piece；
Fig. 6 is the intermediate shape figure of the 1st cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Piece；
Fig. 7 is the recovery shape graph of the 1st cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Piece；
Fig. 8 is the temporary shapes of the 320th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Picture；
Fig. 9 is the intermediate shape of the 320th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Picture；
Figure 10 is the recovery shape of the 320th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Picture；
Figure 11 is the temporary shapes of the 780th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Picture；
Figure 12 is the intermediate shape of the 780th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Picture；
Figure 13 is the recovery shape of the 780th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Picture；
Figure 14 is the temporary shape of the 1084th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Shape picture；
Figure 15 is the intermediate shape of the 1084th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Shape picture；
Figure 16 is the recovery shape of the 1084th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Shape picture.
Specific implementation mode
Specific implementation mode one：Present embodiment is a kind of structural formula of high temperature resistance and long service life shape memory polyimides
For：
Wherein, the value range of the n is 15~27.
Specific implementation mode two：Present embodiment is a kind of preparation method of high temperature resistance and long service life shape memory polyimides
It completes according to the following steps：
One, by 4,4'- bis- (4- amino-benzene oxygens), biphenyl is added in aprotic polar solvent, then is stirred in a nitrogen atmosphere
It mixes to 4,4'- bis- (4- amino-benzene oxygens) biphenyl and is completely dissolved, obtain diamine solution；
The body of the amount and aprotic polar solvent of the substance of 4,4'- bis- (4- amino-benzene oxygens) biphenyl described in step 1
Product is than being (0.18mmoL~0.3mmoL):1mL；
Two, Bisphenol A Type Diether Dianhydride monomer is divided 4 times~6 times and is added in the diamine solution obtained in step 1, then
Room temperature and mixing speed are stirred to react 15h~30h under conditions of being 250r/min~550r/min, obtain the macromolecular of acid anhydride sealing end
Measure polyamic acid；
(4- amino-benzene oxygens) biphenyl of 4,4'- bis- and Bisphenol A Type Diether Dianhydride list in diamine solution described in step 2
The amount ratio of the substance of body is (0.85~1):1；
Three, three (4- aminophenyls) amine are added in the macromolecule polyamic acid of the acid anhydride sealing end obtained in step 2,
It is again 250r/min~550r/min in room temperature and mixing speed, is stirred to react 3h~7h, obtains collosol and gel；It will obtain again
Collosol and gel dry 1h~2h in the vacuum drying chamber that temperature is 50~70 DEG C, obtains the thick collosol and gel of bubble-free；
The amount of three (4- aminophenyls) amine and the substance of Bisphenol A Type Diether Dianhydride monomer in step 2 described in step 3
Than for (2~9):100；
Four, the thick collosol and gel of the bubble-free obtained in step 3 is coated uniformly on clean glass plate, then
It is started to warm up from room temperature to 80 DEG C~100 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min, and is 80 DEG C~100 DEG C in temperature
Lower heat preservation 1h~2h；
130 DEG C~150 DEG C are warming up to from 80 DEG C~100 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and in temperature
Degree is that 1h~2h is kept the temperature at 130 DEG C~150 DEG C；
180 DEG C~200 DEG C are warming up to from 130 DEG C~150 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and in temperature
Degree is that 1h~2h is kept the temperature at 180 DEG C~200 DEG C；
230 DEG C~250 DEG C are warming up to from 180 DEG C~200 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and in temperature
Degree is that 1h~2h is kept the temperature at 230 DEG C~250 DEG C；
280 DEG C~290 DEG C are warming up to from 230 DEG C~250 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and in temperature
Degree is that 1h~2h is kept the temperature at 280 DEG C~290 DEG C；
Room temperature is finally cooled to from 280 DEG C~290 DEG C with the rate of temperature fall of 1 DEG C/min~2 DEG C/min；
The glass plate that will drop to room temperature again is immersed in the solid film on glass plate is made to fall off in distilled water, then uses distilled water
Obtained solid film is rinsed well, finally by the solid film rinsed well under conditions of temperature is 100 DEG C~180 DEG C
300min~400min is heated, high temperature resistance and long service life shape memory polyimides is obtained.
Present embodiment includes following advantageous effect：
One, the T of high temperature resistance and long service life shape memory polyimides prepared by present embodimentgIt is 230 DEG C~236 DEG C, protects
It has demonstrate,proved its shape memory effect and can be applied to high-temperature field；
Two, there is high temperature resistance and long service life shape memory polyimides prepared by present embodiment excellent shape memory to imitate
It answers, and has the very long service life, after cycle more than 1000 times, still keep good shape fixed rate and shape recovery rate；
Three, high temperature resistance and long service life shape memory polyimides prepared by present embodiment has excellent thermodynamic property,
Storage modulus in 60 DEG C of glassy states of room temperature is 2.1GPa-2.6GPa；High temperature (Tg+ 20 DEG C) rubbery state when storage modulus about
For 6.5MPa~7.3MPa, after multiplicating, excellent thermodynamic property is still kept；
Four, point when mass loss of high temperature resistance and long service life shape memory polyimides prepared by present embodiment is 5%
It is 501 DEG C~505 DEG C to solve temperature, and the residual at 800 DEG C is 55.9%~57.3%, illustrates resistance to height prepared by present embodiment
Warm long-life shape memory polyimides has excellent heat resistance.
Specific implementation mode three：One of present embodiment and specific implementation mode two difference are：Described in step 1
Aprotic polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N-Methyl pyrrolidone.Other steps with
Specific implementation mode two is identical.
Specific implementation mode four：One of present embodiment and specific implementation mode two to three difference are：Institute in step 1
The amount of the substance of 4,4'- bis- (4- amino-benzene oxygens) biphenyl stated and the volume ratio of aprotic polar solvent be (0.22mmoL~
0.28mmoL):1mL.Other steps are identical as specific implementation mode two to three.
Specific implementation mode five：One of present embodiment and specific implementation mode two to four difference are：Institute in step 2
(4- amino-benzene oxygens) biphenyl of 4,4'- bis- and the amount ratio of the substance of Bisphenol A Type Diether Dianhydride monomer are in the diamine solution stated
(0.87~0.95):1.Other steps are identical as specific implementation mode two to four.
Specific implementation mode six：One of present embodiment and specific implementation mode two to five difference are：It will in step 3
Three (4- aminophenyls) amine are added in the macromolecule polyamic acid of the acid anhydride sealing end obtained in step 2, then in room gentle agitation
Speed is 300r/min~500r/min, is stirred to react 5h~7h, obtains collosol and gel；Again by obtained collosol and gel in temperature
For dry 1h~2h in 50~60 DEG C of vacuum drying chambers, the thick collosol and gel of bubble-free is obtained.Other steps with it is specific
Embodiment two to five is identical.
Specific implementation mode seven：One of present embodiment and specific implementation mode two to six difference are：It will in step 4
The thick collosol and gel of the bubble-free obtained in step 3 is coated uniformly on clean glass plate, then with 1 DEG C/min~2
DEG C/heating rate of min starts to warm up to 80 DEG C~90 DEG C from room temperature, and keeps the temperature 1h~2h at being 80 DEG C~90 DEG C in temperature；
130 DEG C~140 DEG C are warming up to from 80 DEG C~90 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and in temperature
It is heat preservation 1h~2h at 130 DEG C~140 DEG C；
180 DEG C~190 DEG C are warming up to from 130 DEG C~140 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and in temperature
Degree is that 1h~2h is kept the temperature at 180 DEG C~190 DEG C；
240 DEG C~250 DEG C are warming up to from 180 DEG C~190 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and in temperature
Degree is that 1h~2h is kept the temperature at 240 DEG C~250 DEG C；
285 DEG C~290 DEG C are warming up to from 240 DEG C~250 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and in temperature
Degree is that 1h~2h is kept the temperature at 285 DEG C~290 DEG C；
Room temperature is finally cooled to from 285 DEG C~290 DEG C with the rate of temperature fall of 1 DEG C/min~2 DEG C/min.Other steps and tool
Body embodiment two to six is identical.
Specific implementation mode eight：One of present embodiment and specific implementation mode two to seven difference are：It will in step 4
The glass plate for being down to room temperature is immersed in the solid for making the solid film on glass plate fall off in distilled water, then will be obtained with distilled water
Film is rinsed well, finally by the solid film rinsed well temperature be 150 DEG C~180 DEG C under conditions of heating 350min~
400min obtains high temperature resistance and long service life shape memory polyimides.Other steps are identical as specific implementation mode two to seven.
Specific implementation mode nine：One of present embodiment and specific implementation mode two to eight difference are：Institute in step 3
The amount ratio of three (4- aminophenyls) amine stated and the substance of Bisphenol A Type Diether Dianhydride monomer in step 2 is 7:100.Other steps
It is identical as specific implementation mode two to eight.
Specific implementation mode ten：One of present embodiment and specific implementation mode two to nine difference are：Institute in step 3
The amount ratio of three (4- aminophenyls) amine stated and the substance of Bisphenol A Type Diether Dianhydride monomer in step 2 is 5:100.Other steps
It is identical as specific implementation mode two to nine.
Beneficial effects of the present invention are verified using following embodiment：
Embodiment one：A kind of preparation method of high temperature resistance and long service life shape memory polyimides is to complete according to the following steps
's：
One, 4.475mmol 4,4'- bis- (4- amino-benzene oxygens) biphenyl is added to 20mL N,N-dimethylformamides
In, then stirred in a nitrogen atmosphere to 4,4'- bis- (4- amino-benzene oxygens) biphenyl and be completely dissolved, obtain diamine solution；
Two, 5.0mmol Bisphenol A Type Diether Dianhydride monomers are divided 5 times and is added in the diamine solution obtained in step 1, then
It is stirred to react 20h under conditions of room temperature and mixing speed are 380r/min, obtains the macromolecule polyamic acid of acid anhydride sealing end；
Three, three (4- aminophenyls) amine are added in the macromolecule polyamic acid of the acid anhydride sealing end obtained in step 2,
It is again 300r/min in room temperature and mixing speed, is stirred to react 6h, obtains collosol and gel；Again by obtained collosol and gel in temperature
For dry 2h in 50 DEG C of vacuum drying chambers, the thick collosol and gel of bubble-free is obtained；
The amount of three (4- aminophenyls) amine and the substance of Bisphenol A Type Diether Dianhydride monomer in step 2 described in step 3
Than being 7:100；
Four, the thick collosol and gel of the bubble-free obtained in step 3 is coated uniformly on clean glass plate, then
It is started to warm up from room temperature to 90 DEG C with the heating rate of 1 DEG C/min, and 2h is kept the temperature at being 90 DEG C in temperature；
It is warming up to 130 DEG C from 90 DEG C with the heating rate of 1 DEG C/min again, and 1.5h is kept the temperature at being 130 DEG C in temperature；
It is warming up to 180 DEG C from 130 DEG C with the heating rate of 1 DEG C/min again, and 1.5h is kept the temperature at being 180 DEG C in temperature；
It is warming up to 230 DEG C from 180 DEG C with the heating rate of 1 DEG C/min again, and 1.5h is kept the temperature at being 230 DEG C in temperature；
It is warming up to 280 DEG C from 230 DEG C with the heating rate of 1 DEG C/min again, and 1h is kept the temperature at being 280 DEG C in temperature；
Room temperature is finally cooled to from 280 DEG C with the rate of temperature fall of 1 DEG C/min；
The glass plate that will drop to room temperature again is immersed in the solid film on glass plate is made to fall off in distilled water, then uses distilled water
Obtained solid film is rinsed well, finally heats the solid film rinsed well under conditions of temperature is 180 DEG C
350min obtains high temperature resistance and long service life shape memory polyimides.
As shown in FIG. 1, FIG. 1 is realities for the infrared spectrum of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Apply the infrared spectrogram of the high temperature resistance and long service life shape memory polyimides of the preparation of example one；
From figure 1 it appears that 1785cm-1The absorption peak at place is the asymmetric stretch absorption peak of acid imide carbonyl
(vAs C=O), and 1726cm-1The absorption peak at place is the feature symmetrical stretching vibration peak (v of acid imide carbonylS C=O), 1380cm-1For
Stretching vibration absworption peak (the v of C-N keysC-N), 1113cm-1It is the bending vibration absorption peak (v of imide ringC-O).These features are inhaled
Receive the polyimides that the sample that peak illustrates prepared by embodiment one is height imidizate.
Fissipation factor variation with temperature such as Fig. 2 of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Shown, Fig. 2 is the fissipation factor figure of high temperature resistance and long service life shape memory polyimides prepared by embodiment one；
As can be seen from Figure 2, the T for the high temperature resistance and long service life shape memory polyimides that prepared by embodiment onegIt is 230 DEG C, ensures
Its shape memory effect can be applied to high-temperature field.
Relationship such as Fig. 3 of the storage modulus and temperature of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
It is shown.Fig. 3 is the storage modulus figure of high temperature resistance and long service life shape memory polyimides prepared by embodiment one；
As can be seen from Figure 3, there are two platforms of high and low temperature section in modulus change curve, storage when 60 DEG C of glassy states
Modulus is 2.1GPa；250 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be about 6.5MPa；It is deposited between two platforms
Storage modulus drastically declines, and corresponds to the Glass Transition of material, the change dramatically of this modulus is that polymer has shape
Remember the necessary condition of property.
The thermogravimetric curve of high temperature resistance and long service life shape memory polyimides prepared by embodiment one is as shown in figure 4, Fig. 4 is
The hot weightless picture of high temperature resistance and long service life shape memory polyimides prepared by embodiment one；
As seen from Figure 4, when the mass loss for the high temperature resistance and long service life shape memory polyimides that prepared by embodiment one is 5%
Decomposition temperature be 501 DEG C, residual at 800 DEG C is 55.9%, illustrates high temperature resistance and long service life shape prepared by embodiment one
Remembering polyimides has excellent heat resistance.
The multiple cycle shape recovery process of high temperature resistance and long service life shape memory polyimides prepared by embodiment one, such as the
1 time, the 320th time, the 780th time and the 1084th time process (temporary shapes, intermediate shape and recovery shape) is such as the institutes of Fig. 5~16
Show,
Fig. 5 is the temporary shapes figure of the 1st cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Piece；
Fig. 6 is the intermediate shape figure of the 1st cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Piece；
Fig. 7 is the recovery shape graph of the 1st cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Piece；
Fig. 8 is the temporary shapes of the 320th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Picture；
Fig. 9 is the intermediate shape of the 320th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Picture；
Figure 10 is the recovery shape of the 320th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Picture；
Figure 11 is the temporary shapes of the 780th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Picture；
Figure 12 is the intermediate shape of the 780th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Picture；
Figure 13 is the recovery shape of the 780th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Picture；
Figure 14 is the temporary shape of the 1084th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Shape picture；
Figure 15 is the intermediate shape of the 1084th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Shape picture；
Figure 16 is the recovery shape of the 1084th cycle of high temperature resistance and long service life shape memory polyimides prepared by embodiment one
Shape picture.
From Fig. 5~Figure 16 as it can be seen that the high temperature resistance and long service life shape memory polyimides of the preparation of embodiment one is at more than 1000 times
Still there is the shape fixed rate and shape recovery ratio close to 100% after cycle, there is the long-life.
Embodiment two：A kind of preparation method of high temperature resistance and long service life shape memory polyimides, is complete according to the following steps
At：
One, by 3.82mmol 4,4'- bis- (4- amino-benzene oxygens) biphenyl is added in 20mL n,N-Dimethylformamide,
It is stirred again to 4,4'- bis- (4- amino-benzene oxygens) biphenyl and is completely dissolved in a nitrogen atmosphere, obtain diamine solution；
Two, 4.0mmol Bisphenol A Type Diether Dianhydride monomers are divided 4 times and is added in the diamine solution obtained in step 1, then
It is stirred to react 18h under conditions of room temperature and mixing speed are 250r/min, obtains the macromolecule polyamic acid of acid anhydride sealing end；
Three, three (4- aminophenyls) amine are added in the macromolecule polyamic acid of the acid anhydride sealing end obtained in step 2,
It is again 350r/min in room temperature and mixing speed, is stirred to react 5h, obtains collosol and gel；Again by obtained collosol and gel in temperature
For dry 1h in 50 DEG C of vacuum drying chambers, the thick collosol and gel of bubble-free is obtained；
The amount of three (4- aminophenyls) amine and the substance of Bisphenol A Type Diether Dianhydride monomer in step 2 described in step 3
Than being 3:100；
Four, the thick collosol and gel of the bubble-free obtained in step 3 is coated uniformly on clean glass plate, then
It is started to warm up from room temperature to 80 DEG C with the heating rate of 1 DEG C/min, and 1h is kept the temperature at being 80 DEG C in temperature；
It is warming up to 130 DEG C from 80 DEG C with the heating rate of 1 DEG C/min again, and 1h is kept the temperature at being 130 DEG C in temperature；
It is warming up to 180 DEG C from 130 DEG C with the heating rate of 1 DEG C/min again, and 1h is kept the temperature at being 180 DEG C in temperature；
It is warming up to 230 DEG C from 180 DEG C with the heating rate of 1 DEG C/min again, and 1h is kept the temperature at being 230 DEG C in temperature；
It is warming up to 280 DEG C from 230 DEG C with the heating rate of 1 DEG C/min again, and 1h is kept the temperature at being 280 DEG C in temperature；
Room temperature is finally cooled to from 280 DEG C with the rate of temperature fall of 1 DEG C/min；
The glass plate that will drop to room temperature again is immersed in the solid film on glass plate is made to fall off in distilled water, then uses distilled water
Obtained solid film is rinsed well, finally heats the solid film rinsed well under conditions of temperature is 160 DEG C
300min obtains high temperature resistance and long service life shape memory polyimides.
The T of high temperature resistance and long service life shape memory polyimides prepared by embodiment twogIt is 232 DEG C, ensure that its shape is remembered
Recall effect and can be applied to high-temperature field.High temperature resistance and long service life shape memory polyimides prepared by embodiment two is in 60 DEG C of glassy states
When storage modulus be 2.3GPa；252 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be about 6.7MPa；It is put down at two
Storage modulus drastically declines between platform, corresponds to the Glass Transition of material, the change dramatically of this modulus is polymer
Has the necessary condition of shape memory property.High temperature resistance and long service life shape memory polyimides mass loss prepared by embodiment two
Decomposition temperature when being 5% is 502 DEG C, and the residual at 800 DEG C is 56.3%, illustrates that high temperature resistant prepared by embodiment two is long-lived
Ordering shape memory polyimides has excellent heat resistance.High temperature resistance and long service life shape memory polyamides prepared by embodiment two is sub-
Amine is equally also with the long-life for still keeping excellent shape memory effect after thousands of cycles.
Embodiment three：A kind of preparation method of high temperature resistance and long service life shape memory polyimides, is complete according to the following steps
At：
One, by 3.70mmol 4,4'- bis- (4- amino-benzene oxygens) biphenyl is added in 20mL n,N-Dimethylformamide,
It is stirred again to 4,4'- bis- (4- amino-benzene oxygens) biphenyl and is completely dissolved in a nitrogen atmosphere, obtain diamine solution；
Two, 4.0mmol Bisphenol A Type Diether Dianhydride monomers are divided 4 times and is added in the diamine solution obtained in step 1, then
It is stirred to react 18h under conditions of room temperature and mixing speed are 380r/min, obtains the macromolecule polyamic acid of acid anhydride sealing end；
Three, three (4- aminophenyls) amine are added in the macromolecule polyamic acid of the acid anhydride sealing end obtained in step 2,
It is again 280r/min in room temperature and mixing speed, is stirred to react 5h, obtains collosol and gel；Again by obtained collosol and gel in temperature
For dry 1h in 60 DEG C of vacuum drying chambers, the thick collosol and gel of bubble-free is obtained；
The amount of three (4- aminophenyls) amine and the substance of Bisphenol A Type Diether Dianhydride monomer in step 2 described in step 3
Than being 5:100；
Four, the thick collosol and gel of the bubble-free obtained in step 3 is coated uniformly on clean glass plate, then
It is started to warm up from room temperature to 90 DEG C with the heating rate of 1 DEG C/min, and 2h is kept the temperature at being 90 DEG C in temperature；
It is warming up to 140 DEG C from 90 DEG C with the heating rate of 1 DEG C/min again, and 2h is kept the temperature at being 140 DEG C in temperature；
It is warming up to 190 DEG C from 140 DEG C with the heating rate of 1 DEG C/min again, and 2h is kept the temperature at being 190 DEG C in temperature；
It is warming up to 240 DEG C from 190 DEG C with the heating rate of 1 DEG C/min again, and 1h is kept the temperature at being 240 DEG C in temperature；
It is warming up to 280 DEG C from 240 DEG C with the heating rate of 2 DEG C/min again, and 1h is kept the temperature at being 280 DEG C in temperature；
Room temperature is finally cooled to from 280 DEG C with the rate of temperature fall of 2 DEG C/min；
The glass plate that will drop to room temperature again is immersed in the solid film on glass plate is made to fall off in distilled water, then uses distilled water
Obtained solid film is rinsed well, finally heats the solid film rinsed well under conditions of temperature is 160 DEG C
350min obtains high temperature resistance and long service life shape memory polyimides.
The T of high temperature resistance and long service life shape memory polyimides prepared by embodiment threegIt is 233 DEG C, ensure that its shape is remembered
Recall effect and can be applied to high-temperature field.High temperature resistance and long service life shape memory polyimides prepared by embodiment three is in 60 DEG C of glassy states
When storage modulus be 2.5GPa；253 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be about 6.7MPa；It is put down at two
Storage modulus drastically declines between platform, corresponds to the Glass Transition of material, the change dramatically of this modulus is polymer
Has the necessary condition of shape memory property.High temperature resistance and long service life shape memory polyimides mass loss prepared by embodiment three
Decomposition temperature when being 5% is 502 DEG C, and the residual at 800 DEG C is 56.9%, illustrates that high temperature resistant prepared by embodiment three is long-lived
Ordering shape memory polyimides has excellent heat resistance.High temperature resistance and long service life shape memory polyamides prepared by embodiment three is sub-
Amine is equally also with the long-life for still keeping excellent shape memory effect after thousands of cycles.
Example IV：A kind of preparation method of high temperature resistance and long service life shape memory polyimides, is complete according to the following steps
At：
One, by 4.55mmol 4,4'- bis- (4- amino-benzene oxygens) biphenyl is added in 20mL n,N-dimethylacetamide,
It is stirred again to 4,4'- bis- (4- amino-benzene oxygens) biphenyl and is completely dissolved in a nitrogen atmosphere, obtain diamine solution；
Two, 5.0mmol Bisphenol A Type Diether Dianhydride monomers are divided 5 times and is added in the diamine solution obtained in step 1, then
It is stirred to react 19h under conditions of room temperature and mixing speed are 500r/min, obtains the macromolecule polyamic acid of acid anhydride sealing end；
Three, three (4- aminophenyls) amine are added in the macromolecule polyamic acid of the acid anhydride sealing end obtained in step 2,
It is again 300r/min in room temperature and mixing speed, is stirred to react 6h, obtains collosol and gel；Again by obtained collosol and gel in temperature
For dry 1h in 60 DEG C of vacuum drying chambers, the thick collosol and gel of bubble-free is obtained；
The amount of three (4- aminophenyls) amine and the substance of Bisphenol A Type Diether Dianhydride monomer in step 2 described in step 3
Than being 6:100；
Four, the thick collosol and gel of the bubble-free obtained in step 3 is coated uniformly on clean glass plate, then
It is started to warm up from room temperature to 90 DEG C with the heating rate of 1 DEG C/min, and 2h is kept the temperature at being 90 DEG C in temperature；
It is warming up to 140 DEG C from 90 DEG C with the heating rate of 1 DEG C/min again, and 2h is kept the temperature at being 140 DEG C in temperature；
It is warming up to 180 DEG C from 140 DEG C with the heating rate of 1 DEG C/min again, and 1h is kept the temperature at being 180 DEG C in temperature；
It is warming up to 240 DEG C from 180 DEG C with the heating rate of 1 DEG C/min again, and 2h is kept the temperature at being 240 DEG C in temperature；
It is warming up to 280 DEG C from 240 DEG C with the heating rate of 1 DEG C/min again, and 1h is kept the temperature at being 280 DEG C in temperature；
Room temperature is finally cooled to from 280 DEG C with the rate of temperature fall of 2 DEG C/min；
The glass plate that will drop to room temperature again is immersed in the solid film on glass plate is made to fall off in distilled water, then uses distilled water
Obtained solid film is rinsed well, finally heats the solid film rinsed well under conditions of temperature is 180 DEG C
300min obtains high temperature resistance and long service life shape memory polyimides.
The T of high temperature resistance and long service life shape memory polyimides prepared by example IVgIt is 235 DEG C, ensure that its shape is remembered
Recall effect and can be applied to high-temperature field.High temperature resistance and long service life shape memory polyimides prepared by example IV is in 60 DEG C of glassy states
When storage modulus be 2.5GPa；255 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be about 7.1MPa；It is put down at two
Storage modulus drastically declines between platform, corresponds to the Glass Transition of material, the change dramatically of this modulus is polymer
Has the necessary condition of shape memory property.High temperature resistance and long service life shape memory polyimides mass loss prepared by example IV
Decomposition temperature when being 5% is 504 DEG C, and the residual at 800 DEG C is 57.1%, illustrates that high temperature resistant prepared by example IV is long-lived
Ordering shape memory polyimides has excellent heat resistance.The material still keeps excellent after equally also having thousands of cycles
The long-life of shape memory effect.
Embodiment five：A kind of preparation method of high temperature resistance and long service life shape memory polyimides, is complete according to the following steps
At：
One, by 5.19mmol 4,4'- bis- (4- amino-benzene oxygens) biphenyl is added in 20mL n,N-dimethylacetamide,
It is stirred again to 4,4'- bis- (4- amino-benzene oxygens) biphenyl and is completely dissolved in a nitrogen atmosphere, obtain diamine solution；
Two, 6mmol Bisphenol A Type Diether Dianhydride monomers are divided 6 times and is added in the diamine solution obtained in step 1, then
Room temperature and mixing speed are stirred to react 22h under conditions of being 550r/min, obtain the macromolecule polyamic acid of acid anhydride sealing end；
Three, three (4- aminophenyls) amine are added in the macromolecule polyamic acid of the acid anhydride sealing end obtained in step 2,
It is again 350r/min in room temperature and mixing speed, is stirred to react 7h, obtains collosol and gel；Again by obtained collosol and gel in temperature
For dry 2h in 70 DEG C of vacuum drying chambers, the thick collosol and gel of bubble-free is obtained；
The amount of three (4- aminophenyls) amine and the substance of Bisphenol A Type Diether Dianhydride monomer in step 2 described in step 3
Than being 9:100；
Four, the thick collosol and gel of the bubble-free obtained in step 3 is coated uniformly on clean glass plate, then
It is started to warm up from room temperature to 100 DEG C with the heating rate of 2 DEG C/min, and 2h is kept the temperature at being 100 DEG C in temperature；
It is warming up to 150 DEG C from 100 DEG C with the heating rate of 2 DEG C/min again, and 2h is kept the temperature at being 150 DEG C in temperature；
It is warming up to 200 DEG C from 150 DEG C with the heating rate of 2 DEG C/min again, and 2h is kept the temperature at being 200 DEG C in temperature；
It is warming up to 250 DEG C from 200 DEG C with the heating rate of 2 DEG C/min again, and 2h is kept the temperature at being 250 DEG C in temperature；
It is warming up to 290 DEG C from 250 DEG C with the heating rate of 2 DEG C/min again, and 2h is kept the temperature at being 290 DEG C in temperature；
Room temperature is finally cooled to from 290 DEG C with the rate of temperature fall of 2 DEG C/min；
The glass plate that will drop to room temperature again is immersed in the solid film on glass plate is made to fall off in distilled water, then uses distilled water
Obtained solid film is rinsed well, finally heats the solid film rinsed well under conditions of temperature is 180 DEG C
400min obtains high temperature resistance and long service life shape memory polyimides.
The T of high temperature resistance and long service life shape memory polyimides prepared by embodiment fivegIt is 236 DEG C, ensure that its shape is remembered
Recall effect and can be applied to high-temperature field.High temperature resistance and long service life shape memory polyimides prepared by embodiment five is in 60 DEG C of glassy states
When storage modulus be 2.6GPa；256 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be about 7.1MPa；It is put down at two
Storage modulus drastically declines between platform, corresponds to the Glass Transition of material, the change dramatically of this modulus is polymer
Has the necessary condition of shape memory property.High temperature resistance and long service life shape memory polyimides mass loss prepared by embodiment five
Decomposition temperature when being 5% is 505 DEG C, and the residual at 800 DEG C is 57.3%, illustrates that high temperature resistant prepared by embodiment five is long-lived
Ordering shape memory polyimides has excellent heat resistance.High temperature resistance and long service life shape memory polyamides prepared by embodiment five is sub-
Amine is equally also with the long-life for still keeping excellent shape memory effect after thousands of cycles.
Claims (9)
1. a kind of high temperature resistance and long service life shape memory polyimides, it is characterised in that a kind of high temperature resistance and long service life shape memory polyamides
The structural formula of imines is：
Wherein, the value range of the n is 15~27；
A kind of preparation method of high temperature resistance and long service life shape memory polyimides, is completed according to the following steps：
One, 4,4'- bis- (4- amino-benzene oxygens) biphenyl is added in aprotic polar solvent, then stir in a nitrogen atmosphere to
4,4'- bis- (4- amino-benzene oxygens) biphenyl are completely dissolved, and obtain diamine solution；
The volume ratio of the amount and aprotic polar solvent of the substance of 4,4'- bis- (4- amino-benzene oxygens) biphenyl described in step 1
For (0.18mmoL~0.3mmoL):1mL；
Two, Bisphenol A Type Diether Dianhydride monomer is divided 4 times~6 times and is added in the diamine solution obtained in step 1, then in room temperature
It is stirred to react 15h~30h under conditions of being 250r/min~550r/min with mixing speed, the macromolecule for obtaining acid anhydride sealing end is poly-
Amic acid；
(4- amino-benzene oxygens) biphenyl of 4,4'- bis- and Bisphenol A Type Diether Dianhydride monomer in diamine solution described in step 2
The amount ratio of substance is (0.85~1):1；
Three, three (4- aminophenyls) amine are added in the macromolecule polyamic acid of the acid anhydride sealing end obtained in step 2, then
Room temperature and mixing speed are 250r/min~550r/min, are stirred to react 3h~7h, obtain collosol and gel；The colloidal sol that will be obtained again
Gel dry 1h~2h in the vacuum drying chamber that temperature is 50~70 DEG C, obtains the thick collosol and gel of bubble-free；
The amount ratio of three (4- aminophenyls) amine and the substance of Bisphenol A Type Diether Dianhydride monomer in step 2 described in step 3 is
(2~9):100；
Four, the thick collosol and gel of the bubble-free obtained in step 3 is coated uniformly on clean glass plate, then with 1
DEG C/heating rate of min~2 DEG C/min starts to warm up from room temperature to 80 DEG C~100 DEG C, and in the case where temperature is 80 DEG C~100 DEG C
Keep the temperature 1h~2h；
130 DEG C~150 DEG C are warming up to from 80 DEG C~100 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and is in temperature
1h~2h is kept the temperature at 130 DEG C~150 DEG C；
180 DEG C~200 DEG C are warming up to from 130 DEG C~150 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and is in temperature
1h~2h is kept the temperature at 180 DEG C~200 DEG C；
230 DEG C~250 DEG C are warming up to from 180 DEG C~200 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and is in temperature
1h~2h is kept the temperature at 230 DEG C~250 DEG C；
280 DEG C~290 DEG C are warming up to from 230 DEG C~250 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and is in temperature
1h~2h is kept the temperature at 280 DEG C~290 DEG C；
Room temperature is finally cooled to from 280 DEG C~290 DEG C with the rate of temperature fall of 1 DEG C/min~2 DEG C/min；
The glass plate that will drop to room temperature again is immersed in the solid film on glass plate is made to fall off in distilled water, then with distilled water will
To solid film rinse well, finally by the solid film rinsed well temperature be 100 DEG C~180 DEG C under conditions of heat
300min~400min obtains high temperature resistance and long service life shape memory polyimides.
2. a kind of high temperature resistance and long service life shape memory polyimides according to claim 1, it is characterised in that in step 1
The aprotic polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N-Methyl pyrrolidone.
3. a kind of high temperature resistance and long service life shape memory polyimides according to claim 1, it is characterised in that in step 1
The amount of the substance of described 4,4'- bis- (4- amino-benzene oxygens) biphenyl and the volume ratio of aprotic polar solvent are (0.22mmoL
~0.28mmoL):1mL.
4. a kind of high temperature resistance and long service life shape memory polyimides according to claim 1, it is characterised in that in step 2
(4- amino-benzene oxygens) biphenyl of 4,4'- bis- and the amount ratio of the substance of Bisphenol A Type Diether Dianhydride monomer are in the diamine solution
(0.87~0.95):1.
5. a kind of high temperature resistance and long service life shape memory polyimides according to claim 1, it is characterised in that in step 3
Three (4- aminophenyls) amine are added in the macromolecule polyamic acid of the acid anhydride sealing end obtained in step 2, then in room temperature and stirred
It is 300r/min~500r/min to mix speed, is stirred to react 5h~7h, obtains collosol and gel；Again by obtained collosol and gel in temperature
Degree is dry 1h~2h in 50~60 DEG C of vacuum drying chamber, obtains the thick collosol and gel of bubble-free.
6. a kind of high temperature resistance and long service life shape memory polyimides according to claim 1, it is characterised in that in step 4
The thick collosol and gel of the bubble-free obtained in step 3 is coated uniformly on clean glass plate, then with 1 DEG C/min~2
DEG C/heating rate of min starts to warm up to 80 DEG C~90 DEG C from room temperature, and keeps the temperature 1h~2h at being 80 DEG C~90 DEG C in temperature；
130 DEG C~140 DEG C are warming up to from 80 DEG C~90 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and is in temperature
1h~2h is kept the temperature at 130 DEG C~140 DEG C；
180 DEG C~190 DEG C are warming up to from 130 DEG C~140 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and is in temperature
1h~2h is kept the temperature at 180 DEG C~190 DEG C；
240 DEG C~250 DEG C are warming up to from 180 DEG C~190 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and is in temperature
1h~2h is kept the temperature at 240 DEG C~250 DEG C；
285 DEG C~290 DEG C are warming up to from 240 DEG C~250 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, and is in temperature
1h~2h is kept the temperature at 285 DEG C~290 DEG C；
Room temperature is finally cooled to from 285 DEG C~290 DEG C with the rate of temperature fall of 1 DEG C/min~2 DEG C/min.
7. a kind of high temperature resistance and long service life shape memory polyimides according to claim 1, it is characterised in that in step 4
The glass plate that will drop to room temperature is immersed in the solid film on glass plate is made to fall off in distilled water, then is consolidated what is obtained with distilled water
Body thin film is rinsed well, and the solid film rinsed well is finally heated 350min under conditions of temperature is 150 DEG C~180 DEG C
~400min obtains high temperature resistance and long service life shape memory polyimides.
8. a kind of high temperature resistance and long service life shape memory polyimides according to claim 1, it is characterised in that in step 3
The amount ratio of three (4- aminophenyls) amine and the substance of Bisphenol A Type Diether Dianhydride monomer in step 2 is 7:100.
9. a kind of high temperature resistance and long service life shape memory polyimides according to claim 1, it is characterised in that in step 3
The amount ratio of three (4- aminophenyls) amine and the substance of Bisphenol A Type Diether Dianhydride monomer in step 2 is 5:100.
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| CN104017213A (en) * | 2014-06-19 | 2014-09-03 | 冷劲松 | Shape memory polyether imide with high glass-transition temperature and preparation method thereof |
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