CN108641355A - A kind of high-modulus shape memory composite polyimide material and preparation method thereof - Google Patents
A kind of high-modulus shape memory composite polyimide material and preparation method thereof Download PDFInfo
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- CN108641355A CN108641355A CN201810381437.2A CN201810381437A CN108641355A CN 108641355 A CN108641355 A CN 108641355A CN 201810381437 A CN201810381437 A CN 201810381437A CN 108641355 A CN108641355 A CN 108641355A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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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
- C08G73/1067—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
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Abstract
A kind of high-modulus shape memory composite polyimide material and preparation method thereof, it is related to a kind of shape memory composite polyimide material and preparation method thereof.The object of the invention will solve at 100 DEG C of existing shape memory polyimides storage modulus and generally be less than 2GPa, and modulus is generally less than the relatively low problems of 10MPa when glass transition under high temperature.Method：One, diamine solution is prepared；Two, polyamic acid is prepared；Three, carbon cloth is impregnated into polyamic acid solution；Four, hot-imide obtains the carbon cloth containing polyimides；Five, it cleans, it is dry.High-modulus shape memory composite polyimide material T prepared by the present inventiongIt it is 312 DEG C~340 DEG C, in TgStorage modulus when 20 DEG C of glassy states is 4.5GPa~3.9GPa；In TgStorage modulus when+10 DEG C of rubbery states is 2.5~1.9GPa.The present invention obtains high-modulus shape memory composite polyimide material.
Description
Technical field
The present invention relates to a kind of high-modulus shape memory composite polyimide materials and preparation method thereof.
Background technology
In outer force effect when shape-memory polymer (shape memory polymers, SMP) typically refers to higher temperature
Its original shape can be changed down, its temporary shapes can be fixed after cooling；It can restore the polymer of original shape when heating up again.It is poly-
Acid imide (polyimide, PI) has many advantages, such as high mechanical properties, radiation resistance, is widely used to aerospace, micro- electricity at present
The fields such as son, machinery.Shape memory polyimides organically combines the excellent properties of polyimides and shape memory effect, too
There is important application prospect in the fields such as empty deployable structure, satellite aileron, aero propulsion device.
However, the mechanical property of shape memory polyimides is still not high enough at present.Such as most shape memory polyimides
Storage modulus is generally less than 2GPa at 100 DEG C, and transfer of shapes temperature is higher than glass transition temperature (Tg), but in this high temperature
When its storage modulus generally be less than 10MPa.Shape memory polyimides lower mechanical property when shape changes temperature makes it
It is difficult to generate sufficiently large motive force, seriously limits its practical application.
Invention content
When the invention aims to solve existing shape memory polyimides storage modulus, especially shape recovery process
Storage modulus it is not high, the restoring force of generation is relatively low, it is difficult to the problem of direct practical application, and provide it is a kind of in practical applications
High-modulus shape memory polyimides with broad prospect of application and preparation method thereof.
A kind of high-modulus shape memory composite polyimide material of the present invention, by shape memory polyimides and carbon fiber
Cloth is made；The shape memory polyimides is prepared by diamines and dianhydride；The diamines is 2- (4- aminophenyls)-
5- An base Ben Bing oxazoles；The dianhydride is Bisphenol A Type Diether Dianhydride.
The carbon cloth is commercial goods.
A kind of preparation method of high-modulus shape memory composite polyimide material of the present invention, is complete according to the following steps
At：
One, diamines is added in aprotic polar solvent, then is stirred to diamines under the nitrogen atmosphere of room gently dried
It is completely dissolved, obtains diamine solution；
The amount of the diamines substance and the volume ratio of aprotic polar solvent are 0.05mol:(100mL~200mL)；
Two, dianhydride is added in diamine solution, then in the item that room temperature and mixing speed are 300r/min~800r/min
Polymerisation 5h~30h under part, obtains polyamic acid solution；
The molar ratio of the dianhydride and diamines is 0.90:1~1.10:1；
Three, carbon cloth is added to immersion 4h~60h in polyamic acid solution, obtains the fiber for being impregnated with polyamic acid
Cloth；
Four, it will be placed on clean glass plate, be subsequently placed in baking oven, then right immersed with the carbon cloth of polyamic acid
Baking oven carries out temperature programming, completes hot-imide, obtains high-modulus shape memory composite polyimide material；
Wherein, the condition of baking oven temperature programming is：
With the heating rate of 1 DEG C/min~2 DEG C/min from room temperature to 70 DEG C~90 DEG C, then protected at 70 DEG C~90 DEG C
Warm 2h~3h；
150 DEG C~170 DEG C are warming up to from 70 DEG C~90 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, then 150
DEG C~170 DEG C at keep the temperature 2h~3h；
Again 190 DEG C~210 DEG C are warming up to from 150 DEG C~170 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min, then
2h~3h is kept the temperature at 190 DEG C~210 DEG C；
Again 240 DEG C~260 DEG C are warming up to from 190 DEG C~210 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min, then
240 DEG C~260 DEG C heat preservation 1h~2h；
Again 280 DEG C~300 DEG C are warming up to from 240 DEG C~260 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min, then
280 DEG C~300 DEG C heat preservation 1h~2h；
Room temperature is cooled to from 280 DEG C~300 DEG C with the rate of temperature fall of 1 DEG C/min~2 DEG C/min again；
Five, the glass plate containing high-modulus shape memory composite polyimide material is placed in distilled water, shape is made to remember
Recall composite polyimide material to fall off from glass plate, reuse distilled water and rinsed well, then is done at being 120 DEG C in temperature
Dry 3h obtains high-modulus shape memory composite polyimide material；
The diamines is 2- (4- aminophenyls) -5- An base Ben Bing oxazoles；Dianhydride is Bisphenol A Type Diether Dianhydride.
The present invention includes following advantageous effect：
One, the present invention prepares the shape memory polyimides composite wood that the storage modulus at 100 DEG C is more than 6GPa for the first time
Material is no more than the shape memory polyimide material of 2GPa, this novel shape note relative to storage modulus at existing 100 DEG C
Larger motive force can be generated in recovery of shape by recalling composite polyimide material, and the metallic plate overturning of covering thereon can be made to move
It is dynamic, to make shape memory polyimides that there is more direct actual application prospect.The present invention is expected to further expand shape
Remember the application range field of polyimides；
Two, the present invention is prepared for the first time higher than its glass transition temperature (Tg) when storage modulus be more than 1GPa shape
Composite polyimide material is remembered, relative to existing in TgStorage modulus is usually less than the shape note of 10MPa when temperatures above
Recall polyimide material, the present invention makes shape memory polyimides have the very big possibility of practical application；
Three, carbon cloth is immersed in polyamic acid by high-modulus shape memory composite polyimide material prepared by the present invention
After in solution, solidification can be prepared by, and preparation process is simple, be advantageously implemented industrialization；The material has preferable shape memory
Performance, shape fixed rate are more than 95%, and shape recovery rate is more than 80%.
Description of the drawings
Fig. 1 is the macro morphology figure of high-modulus shape memory composite polyimide material prepared by embodiment one；
Fig. 2 is the enlarged structure of the high-modulus shape memory composite polyimide material of the preparation of embodiment one under the microscope
Figure；
Fig. 3 is the infrared spectrogram of high-modulus shape memory composite polyimide material prepared by embodiment one；
Fig. 4 is the fissipation factor figure of shape memory polyimides bulk material prepared by embodiment one；
Fig. 5 is the storage modulus figure of shape memory polyimides bulk material prepared by embodiment one；
Fig. 6 is the fissipation factor figure of high-modulus shape memory composite polyimide material prepared by embodiment one；
Fig. 7 is the storage modulus figure of high-modulus shape memory composite polyimide material prepared by embodiment one；
Fig. 8 is the temporary shapes of high-modulus shape memory composite polyimide material prepared by embodiment one；
Fig. 9 is the shape of high-modulus shape memory composite polyimide material 3s in 380 DEG C of thermal station prepared by embodiment one
Shape replys figure；
Figure 10 is the shape of high-modulus shape memory composite polyimide material 5s in 380 DEG C of thermal station prepared by embodiment one
Shape replys figure；
Figure 11 is the shape of high-modulus shape memory composite polyimide material 8s in 380 DEG C of thermal station prepared by embodiment one
Shape replys figure.
Specific implementation mode
Specific implementation mode one：A kind of high-modulus shape memory composite polyimide material of present embodiment, by shape
Memory polyimides and carbon cloth are made；The shape memory polyimides is prepared by diamines and dianhydride；Described
Diamines is 2- (4- aminophenyls) -5- An base Ben Bing oxazoles；The dianhydride is Bisphenol A Type Diether Dianhydride.
Specific implementation mode two：The present embodiment is different from the first embodiment in that：Dianhydride：The amount of the substance of diamines
The ratio between be 0.90:1~1.10:1.It is other same as the specific embodiment one.
Specific implementation mode three：A kind of preparation side of high-modulus shape memory composite polyimide material of present embodiment
Method is to complete according to the following steps：
One, diamines is added in aprotic polar solvent, then is stirred to diamines under the nitrogen atmosphere of room gently dried
It is completely dissolved, obtains diamine solution；
The amount of the diamines substance and the volume ratio of aprotic polar solvent are 0.05mol:(100mL~200mL)；
Two, dianhydride is added in diamine solution, then in the item that room temperature and mixing speed are 300r/min~800r/min
Polymerisation 5h~30h under part, obtains polyamic acid solution；
The molar ratio of the dianhydride and diamines is 0.90:1~1.10:1；
Three, carbon cloth is added to immersion 4h~60h in polyamic acid solution, obtains the fiber for being impregnated with polyamic acid
Cloth；
Four, it will be placed on clean glass plate, be subsequently placed in baking oven, then right immersed with the carbon cloth of polyamic acid
Baking oven carries out temperature programming, completes hot-imide, obtains high-modulus shape memory composite polyimide material；
Wherein, the condition of baking oven temperature programming is：
With the heating rate of 1 DEG C/min~2 DEG C/min from room temperature to 70 DEG C~90 DEG C, then protected at 70 DEG C~90 DEG C
Warm 2h~3h；
150 DEG C~170 DEG C are warming up to from 70 DEG C~90 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, then 150
DEG C~170 DEG C at keep the temperature 2h~3h；
Again 190 DEG C~210 DEG C are warming up to from 150 DEG C~170 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min, then
2h~3h is kept the temperature at 190 DEG C~210 DEG C；
Again 240 DEG C~260 DEG C are warming up to from 190 DEG C~210 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min, then
240 DEG C~260 DEG C heat preservation 1h~2h；
Again 280 DEG C~300 DEG C are warming up to from 240 DEG C~260 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min, then
280 DEG C~300 DEG C heat preservation 1h~2h；
Room temperature is cooled to from 280 DEG C~300 DEG C with the rate of temperature fall of 1 DEG C/min~2 DEG C/min again；
Five, the glass plate containing high-modulus shape memory composite polyimide material is placed in distilled water, shape is made to remember
Recall composite polyimide material to fall off from glass plate, reuse distilled water and rinsed well, then is done at being 120 DEG C in temperature
Dry 3h obtains high-modulus shape memory composite polyimide material；
The diamines is 2- (4- aminophenyls) -5- An base Ben Bing oxazoles；Dianhydride is Bisphenol A Type Diether Dianhydride.
Specific implementation mode four：Present embodiment is unlike specific implementation mode three：Non- matter described in step 1
Sub- polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N-Methyl pyrrolidone.Other and specific implementation
Mode three is identical.
Specific implementation mode five：Present embodiment is unlike specific implementation mode three：Diamines described in step 1
The amount of substance and the volume ratio of aprotic polar solvent are 0.05mol:180mL.It is other to be the same as the specific implementation mode 3.
Specific implementation mode six：Present embodiment is unlike specific implementation mode three：Diamines described in step 1
The amount of substance and the volume ratio of aprotic polar solvent are 0.05mol:190mL.It is other to be the same as the specific implementation mode 3.
Specific implementation mode seven：Present embodiment is unlike specific implementation mode three：Diamines described in step 1
The amount of substance and the volume ratio of aprotic polar solvent are 0.05mol:200mL.It is other to be the same as the specific implementation mode 3.
Specific implementation mode eight：Present embodiment is unlike specific implementation mode three：Baking oven program liter in step 4
Temperature condition be：
With the heating rate of 1 DEG C/min from room temperature to 80 DEG C, then 2h is kept the temperature at 80 DEG C；
It is warming up to 160 DEG C from 80 DEG C with the heating rate of 2 DEG C/min again, then 2h is kept the temperature at 160 DEG C；
It is warming up to 190 DEG C from 160 DEG C with the heating rate of 1 DEG C/min again, then 2h is kept the temperature at 190 DEG C；
It is warming up to 250 DEG C from 190 DEG C with the heating rate of 1 DEG C/min again, then keeps the temperature 1h at 250 DEG C；
It is warming up to 280 DEG C from 260 DEG C with the heating rate of 1 DEG C/min again, then keeps the temperature 1h at 280 DEG C；
Room temperature is cooled to from 280 DEG C~300 DEG C with the rate of temperature fall of 1 DEG C/min~2 DEG C/min again.
It is other to be the same as the specific implementation mode 3.
Specific implementation mode nine：Present embodiment is unlike specific implementation mode three：Baking oven program liter in step 4
Temperature condition be：
With the heating rate of 1 DEG C/min from room temperature to 80 DEG C, then 2h is kept the temperature at 80 DEG C；
It is warming up to 160 DEG C from 80 DEG C with the heating rate of 2 DEG C/min again, then 2h is kept the temperature at 160 DEG C；
It is warming up to 190 DEG C from 160 DEG C with the heating rate of 1 DEG C/min again, then 2h is kept the temperature at 190 DEG C；
It is warming up to 250 DEG C from 190 DEG C with the heating rate of 1 DEG C/min again, then keeps the temperature 1h at 250 DEG C；
It is warming up to 280 DEG C from 260 DEG C with the heating rate of 1 DEG C/min again, then keeps the temperature 1h at 280 DEG C,
Room temperature is cooled to from 280 DEG C~300 DEG C with the rate of temperature fall of 1 DEG C/min~2 DEG C/min again.
It is other to be the same as the specific implementation mode 3.
Specific implementation mode ten：Present embodiment is unlike specific implementation mode three：Baking oven program liter in step 4
Temperature condition be：
With the heating rate of 1 DEG C/min from room temperature to 80 DEG C, then 2h is kept the temperature at 80 DEG C；
It is warming up to 160 DEG C from 80 DEG C with the heating rate of 2 DEG C/min again, then 2h is kept the temperature at 160 DEG C；
It is warming up to 190 DEG C from 160 DEG C with the heating rate of 2 DEG C/min again, then 2h is kept the temperature at 190 DEG C；
It is warming up to 250 DEG C from 190 DEG C with the heating rate of 1 DEG C/min again, then keeps the temperature 1h at 250 DEG C；
It is warming up to 300 DEG C from 250 DEG C with the heating rate of 2 DEG C/min again, then keeps the temperature 1h at 300 DEG C；
Room temperature is cooled to from 280 DEG C~300 DEG C with the rate of temperature fall of 1 DEG C/min~2 DEG C/min again.
It is other to be the same as the specific implementation mode 3.
Specific implementation mode 11：Present embodiment is unlike specific implementation mode three：Baking oven program in step 4
The condition of heating is：
With the heating rate of 1 DEG C/min from room temperature to 80 DEG C, then 2h is kept the temperature at 80 DEG C；
It is warming up to 160 DEG C from 80 DEG C with the heating rate of 1 DEG C/min again, then 2h is kept the temperature at 160 DEG C；
It is warming up to 190 DEG C from 160 DEG C with the heating rate of 1 DEG C/min again, then 2h is kept the temperature at 190 DEG C；
It is warming up to 250 DEG C from 190 DEG C with the heating rate of 2 DEG C/min again, then keeps the temperature 1h at 250 DEG C；
Again 290 DEG C are warming up to from 250 DEG C with the heating rate of 2 DEG C/min.1h is kept the temperature at 290 DEG C again；
Room temperature is cooled to from 280 DEG C~300 DEG C with the rate of temperature fall of 1 DEG C/min~2 DEG C/min again.
It is other to be the same as the specific implementation mode 3.
Specific implementation mode 12：Present embodiment is unlike specific implementation mode three：Step 3 kind carbon cloth
10h~60h is impregnated in polyamic acid solution.It is other to be the same as the specific implementation mode 3.
Beneficial effects of the present invention are verified using following embodiment：
Embodiment one：A kind of preparation method of high-modulus shape memory composite polyimide material is to complete according to the following steps
's：
One, the 2- of 0.05mol (4- aminophenyls) -5- An base Ben Bing oxazoles are added to 180mL N, N- dimethylacetamides
It in amine, then stirs under the nitrogen atmosphere of room gently dried and is completely dissolved to bis- (4- amino-benzene oxygens) benzene of 1,3-, obtain diamines
Solution；
Two, 0.05mol Bisphenol A Type Diether Dianhydrides are added in the diamine solution obtained in step 1, then in room temperature and
Polymerisation 15h under nitrogen atmosphere, obtains polyamic acid；
Three, gained polyamic acid is poured into container, then carbon cloth is put into wherein, is impregnated 40 hours；
Four, it will be placed on clean glass plate, be subsequently placed in baking oven immersed with the carbon cloth of polyamic acid, then will
Baking oven, from room temperature to 90 DEG C, then keeps the temperature 2h with the heating rate of 1 DEG C/min at being 90 DEG C in temperature, then with 1 DEG C/min's
Heating rate is warming up to 150 DEG C from 90 DEG C, then 2h is kept the temperature at being 150 DEG C in temperature, then with the heating rate of 1 DEG C/min from 150
190 DEG C DEG C are warming up to, then 2h is kept the temperature at being 190 DEG C in temperature, then 250 are warming up to from 190 DEG C with the heating rate of 1 DEG C/min
DEG C, then be 250 DEG C in temperature and keep the temperature 1h, then 300 DEG C are warming up to from 250 DEG C with the heating rate of 1 DEG C/min, then be in temperature
300 DEG C of heat preservation 1h, complete hot-imide, obtain the glass plate containing high-modulus shape memory composite polyimide material；
Five, the glass plate containing high-modulus shape memory composite polyimide material is placed in distilled water, makes high-modulus
Shape memory composite polyimide material falls off from glass plate, reuses distilled water and rinses film well, then is in temperature
Dry 3h, obtains high-modulus shape memory composite polyimide material at 120 DEG C.
As a comparison, 20ml polyamic acids are directly placed on clean glass plate by the present embodiment, are subsequently placed in baking oven
In, then by baking oven with the heating rate of 1 DEG C/min~2 DEG C/min from room temperature to 70 DEG C~90 DEG C, then at 70 DEG C~90 DEG C
Lower heat preservation 2h~3h, then it is warming up to 150 DEG C~170 DEG C from 70 DEG C~90 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min, then
2h~3h is kept the temperature at 150 DEG C~170 DEG C, then is warming up to from 150 DEG C~170 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min
190 DEG C~210 DEG C, then 2h~3h is kept the temperature at 190 DEG C~210 DEG C, then with the heating rate of 1 DEG C/min~2 DEG C/min from 190
DEG C~210 DEG C be warming up to 240 DEG C~260 DEG C, then keep the temperature 1h~2h at 240 DEG C~260 DEG C, then with 1 DEG C/min~2 DEG C/min's
Heating rate is warming up to 280 DEG C~300 DEG C from 240 DEG C~260 DEG C, then 1h~2h is kept the temperature at 280 DEG C~300 DEG C, completes hot acyl
Imidization obtains shape memory polyimides bulk material；
High-modulus shape memory composite polyimide material macro morphology manufactured in the present embodiment is as shown in Figure 1, wherein carbon
Fiber cloth is no longer loose soft shape, but becomes fine and close firm plank；Carbon cloth surface is also no longer original
Dead color, but be provided with certain metallic luster.
The amplification pattern such as Fig. 2 of high-modulus shape memory composite polyimide material manufactured in the present embodiment under the microscope
Shown, carbon cloth is worked out by crisscross carbon fiber bundle, its is crisscross still clear after forming composite material
It is variable, wherein the blank staggeredly pointed out is filled by Kapton.
High-modulus shape memory composite polyimide material prepared by embodiment one is tested using infrared spectrometer,
Fig. 3 is its infrared spectrogram；As can be seen from Figure 3, these characteristic absorption peaks illustrate that high-modulus shape memory prepared by embodiment one is poly-
Acid imide composite material is the polyimides of height polyamides Asia.
Fig. 4 be embodiment one prepare the shape memory polyimides bulk material without impregnation of carbon fibers cloth loss because
Subgraph；As can be seen from Figure 4 the T of shape memory polyimides bulk materialgIt is 245 DEG C.
Fig. 5 is the storage mould of the shape memory polyimides bulk material without impregnation of carbon fibers cloth prepared by embodiment one
Spirogram；As can be seen from Figure 5, there is glassy state and two platforms of rubbery state in storage modulus change curve, and shape memory polyamides is sub-
Storage modulus of the amine bulk material at 100 DEG C is 1.53GPa, 225 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be
1.10GPa；In 255 DEG C of (T of rubbery stateg+ 10 DEG C) rubbery state when storage modulus be 5.10MPa.
Fig. 6 is the fissipation factor figure of high-modulus shape memory composite polyimide material prepared by embodiment one；From Fig. 6
It can be seen that the T of high-modulus shape memory composite polyimide materialgIt is 325 DEG C.Relative to the shape for being not impregnated with carbon cloth
Remember polyimides bulk material, the T of high-modulus shape memory composite polyimide materialg80 DEG C are increased, is further increased
The high temperature resistant degree of shape memory polyimide material.
Fig. 7 is the storage modulus figure of high-modulus shape memory composite polyimide material prepared by embodiment one；It can from Fig. 7
Know, glassy state and two platforms of rubbery state equally also occurs in storage modulus change curve.But high-modulus shape memory polyamides
Storage modulus of the imines composite material at 100 DEG C is 6.59GPa, is 4.3 times of its bulk material；305℃(Tg- 20 DEG C) glass
Storage modulus when glass state is 4.23GPa, is 3.85 times of its bulk material；In 335 DEG C of (T of rubbery stateg+ 10 DEG C) rubbery state when
Storage modulus be 2.39GPa, be 468 times of its bulk material.These results illustrate that carbon cloth keeps shape memory polyamides sub-
The mechanical moduli of amine is improved significantly.
Fig. 8 is the temporary shapes of high-modulus shape memory composite polyimide material prepared by embodiment one, i.e., in high temperature
After lower change shape, obtained temporary shapes are fixed at room temperature；One of metal aluminum sheet is placed on above composite material.
Fig. 9 is the high-modulus shape memory composite polyimide material for preparing of embodiment one shape after 3s in 380 DEG C of thermal station
The situation of shape recovery process, it is seen that it can push aluminium sheet open in shape recovery process；
Figure 10 is the high-modulus shape memory composite polyimide material for preparing of embodiment one shape after 5s in 380 DEG C of thermal station
The situation of shape recovery process, it is seen that it can further push aluminium sheet to upright open in shape recovery process；
Figure 11 is the high-modulus shape memory composite polyimide material of the preparation of embodiment one after the 8s in 380 DEG C of thermal station
The situation of shape recovery process, it is seen that it can further push over aluminium sheet in shape recovery process；
From Fig. 8 to Figure 10 it is found that high-modulus shape memory composite polyimide material prepared by embodiment one is returned in shape
Larger motive force can be generated during multiple, aluminium sheet is flicked to and pushed overturning, in following practical application specifically very
Important application prospect.In addition, high-modulus shape memory composite polyimide material prepared by embodiment one has preferable shape
Shape memory performance, shape fixed rate are 95%, shape recovery rate 80%.
Embodiment two：A kind of preparation method of high-modulus shape memory composite polyimide material is to complete according to the following steps
's：
One, 0.05mol 2- (4- aminophenyls) -5- An base Ben Bing oxazoles are added to 190mL N, N- dimethylacetamides
It in amine, then is stirred under the nitrogen atmosphere of room gently dried to being completely dissolved, obtains diamine solution；
Two, 0.05mol Bisphenol A Type Diether Dianhydrides are added in the diamine solution obtained in step 1, then in room temperature and
Polymerisation 16h under nitrogen atmosphere, obtains polyamic acid；
Three, gained polyamic acid is poured into container, then carbon cloth is put into wherein, is impregnated 36 hours；
Four, it will be placed on clean glass plate, be subsequently placed in baking oven immersed with the carbon cloth of polyamic acid, then will
Baking oven, from room temperature to 80 DEG C, then keeps the temperature 2h with the heating rate of 1 DEG C/min at being 80 DEG C in temperature, then with 2 DEG C/min's
Heating rate is warming up to 160 DEG C from 80 DEG C, then 2h is kept the temperature at being 160 DEG C in temperature, then with the heating rate of 1 DEG C/min from 160
190 DEG C DEG C are warming up to, then 2h is kept the temperature at being 190 DEG C in temperature, then 250 are warming up to from 190 DEG C with the heating rate of 1 DEG C/min
DEG C, then be 250 DEG C in temperature and keep the temperature 1h, then 300 DEG C are warming up to from 250 DEG C with the heating rate of 1 DEG C/min, then be in temperature
300 DEG C of heat preservation 1h, complete hot-imide, obtain the glass plate containing high-modulus shape memory composite polyimide material；
Five, the glass plate containing high-modulus shape memory composite polyimide material is placed in water, makes high-modulus shape
Memory composite polyimide material film falls off from glass plate, reuses distilled water and rinses film well, then is in temperature
Dry 3h, obtains high-modulus shape memory composite polyimide material at 100 DEG C.
The T of high-modulus shape memory composite polyimide material prepared by embodiment twogIt is 320 DEG C, ensure that embodiment
The two high-modulus shape memory composite polyimide materials prepared can be applied to high-temperature shape-memory field；Prepared by embodiment two
High-modulus shape memory composite polyimide material is in 300 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 4.36GPa；
330 DEG C of (T of high temperatureg+ 10 DEG C) rubbery state when storage modulus be 2.28GPa.In addition, high-modulus shape note prepared by embodiment two
Recalling composite polyimide material also has preferable shape-memory properties, shape fixed rate 96%, shape recovery rate 81%.
Embodiment three：A kind of preparation method of high-modulus shape memory composite polyimide material is to complete according to the following steps
's：
One, 0.05mol 2- (4- aminophenyls) -5- An base Ben Bing oxazoles are added to 150mL N, N- dimethylacetamides
It in amine, then stirs under the nitrogen atmosphere of room gently dried and is completely dissolved to 2- (4- aminophenyls) -5- ammonia base the third oxazoles of benzene, obtain
To diamine solution；
Two, 0.05mol Bisphenol A Type Diether Dianhydrides are added in the diamine solution obtained in step 1, then in room temperature and
Polymerisation 17h under nitrogen atmosphere, obtains polyamic acid；
Three, gained polyamic acid is poured into container, then carbon cloth is put into wherein, is impregnated 38 hours；
Four, it will be placed on clean glass plate, be subsequently placed in baking oven immersed with the carbon cloth of polyamic acid, then will
Baking oven, from room temperature to 80 DEG C, then keeps the temperature 2h with the heating rate of 1 DEG C/min at being 80 DEG C in temperature, then with 2 DEG C/min's
Heating rate is warming up to 160 DEG C from 80 DEG C, then 2h is kept the temperature at being 160 DEG C in temperature, then with the heating rate of 2 DEG C/min from 160
190 DEG C DEG C are warming up to, then 2h is kept the temperature at being 190 DEG C in temperature, then 250 are warming up to from 190 DEG C with the heating rate of 1 DEG C/min
DEG C, then be 250 DEG C in temperature and keep the temperature 1h, then 300 DEG C are warming up to from 250 DEG C with the heating rate of 1 DEG C/min, then be in temperature
300 DEG C of heat preservation 1h, complete hot-imide, obtain the glass plate containing high-modulus shape memory composite polyimide material；
Five, the glass plate containing high-modulus shape memory composite polyimide material is placed in water, makes high-modulus shape
Memory composite polyimide material film falls off from glass plate, reuses distilled water and rinses film well, then is in temperature
Dry 3h, obtains high-modulus shape memory composite polyimide material at 100 DEG C.
The T of high-modulus shape memory composite polyimide material prepared by embodiment threegIt is 328 DEG C, ensure that embodiment
The three high-modulus shape memory composite polyimide materials prepared can be applied to high-temperature shape-memory field；Prepared by embodiment three
High-modulus shape memory composite polyimide material is in 308 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 4.39GPa；
338 DEG C of (T of high temperatureg+ 10 DEG C) rubbery state when storage modulus be 2.10GPa.In addition, high-modulus shape note prepared by embodiment three
Recalling composite polyimide material also has preferable shape-memory properties, shape fixed rate 97%, shape recovery rate 84%.
Example IV：A kind of preparation method of high-modulus shape memory composite polyimide material is to complete according to the following steps
's：
One, 0.05mol 2- (4- aminophenyls) -5- An base Ben Bing oxazoles are added to 160mL N, N- dimethylacetamides
It in amine, then stirs under the nitrogen atmosphere of room gently dried and is completely dissolved to 2- (4- aminophenyls) -5- ammonia base the third oxazoles of benzene, obtain
To diamine solution；
Two, 0.055mol Bisphenol A Type Diether Dianhydrides are added in the diamine solution obtained in step 1, then in room temperature and
Polymerisation 10h under nitrogen atmosphere, obtains polyamic acid；
Three, gained polyamic acid is poured into container, then carbon cloth is put into wherein, is impregnated 40 hours；
Four, it will be placed on clean glass plate, be subsequently placed in baking oven immersed with the carbon cloth of polyamic acid, then will
Baking oven, from room temperature to 80 DEG C, then keeps the temperature 2h with the heating rate of 1 DEG C/min at being 80 DEG C in temperature, then with 2 DEG C/min's
Heating rate is warming up to 160 DEG C from 80 DEG C, then 2h is kept the temperature at being 160 DEG C in temperature, then with the heating rate of 2 DEG C/min from 160
190 DEG C DEG C are warming up to, then 2h is kept the temperature at being 190 DEG C in temperature, then 250 are warming up to from 190 DEG C with the heating rate of 2 DEG C/min
DEG C, then be 250 DEG C in temperature and keep the temperature 1h, then 300 DEG C are warming up to from 250 DEG C with the heating rate of 1 DEG C/min, then be in temperature
300 DEG C of heat preservation 1h, complete hot-imide, obtain the glass plate containing high-modulus shape memory composite polyimide material；
Five, the glass plate containing high-modulus shape memory composite polyimide material is placed in water, makes high-modulus shape
Memory composite polyimide material film falls off from glass plate, reuses distilled water and rinses film well, then is in temperature
Dry 3h, obtains high-modulus shape memory composite polyimide material at 110 DEG C.
The T of high-modulus shape memory composite polyimide material prepared by example IVgIt is 317 DEG C, ensure that embodiment
The four high-modulus shape memory composite polyimide materials prepared can be applied to high-temperature shape-memory field；Prepared by example IV
High-modulus shape memory composite polyimide material is in 297 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 4.41GPa；
327 DEG C of (T of high temperatureg+ 10 DEG C) rubbery state when storage modulus be 2.30GPa.In addition, high-modulus shape note prepared by example IV
Recalling composite polyimide material also has preferable shape-memory properties, shape fixed rate 98%, shape recovery rate 85%.
Embodiment five：A kind of preparation method of high-modulus shape memory composite polyimide material is to complete according to the following steps
's：
One, 0.05mol 2- (4- aminophenyls) -5- An base Ben Bing oxazoles are added to 170mL N, N- dimethylacetamides
It in amine, then stirs under the nitrogen atmosphere of room gently dried and is completely dissolved to 2- (4- aminophenyls) -5- ammonia base the third oxazoles of benzene, obtain
To diamine solution；
Two, 0.048mol Bisphenol A Type Diether Dianhydrides are added in the diamine solution obtained in step 1, then in room temperature and
Polymerisation 19h under nitrogen atmosphere, obtains polyamic acid；
Three, gained polyamic acid is poured into container, then carbon cloth is put into wherein, is impregnated 32 hours；
Four, it will be placed on clean glass plate, be subsequently placed in baking oven immersed with the carbon cloth of polyamic acid, then will
Baking oven, from room temperature to 80 DEG C, then keeps the temperature 2h with the heating rate of 1 DEG C/min at being 80 DEG C in temperature, then with 2 DEG C/min's
Heating rate is warming up to 160 DEG C from 80 DEG C, then 2h is kept the temperature at being 160 DEG C in temperature, then with the heating rate of 2 DEG C/min from 160
190 DEG C DEG C are warming up to, then 2h is kept the temperature at being 190 DEG C in temperature, then 250 are warming up to from 190 DEG C with the heating rate of 2 DEG C/min
DEG C, then be 250 DEG C in temperature and keep the temperature 1h, then 300 DEG C are warming up to from 250 DEG C with the heating rate of 1 DEG C/min, then be in temperature
300 DEG C of heat preservation 1h, complete hot-imide, obtain the glass plate containing high-modulus shape memory composite polyimide material；
Five, the glass plate containing high-modulus shape memory composite polyimide material is placed in water, makes high-modulus shape
Memory composite polyimide material film falls off from glass plate, reuses distilled water and rinses film well, then is in temperature
Dry 3h, obtains high-modulus shape memory composite polyimide material at 110 DEG C.
The T of high-modulus shape memory composite polyimide material prepared by embodiment fivegIt is 326 DEG C, ensure that embodiment
The five high-modulus shape memory composite polyimide materials prepared can be applied to high-temperature shape-memory field；Prepared by embodiment five
High-modulus shape memory composite polyimide material is in 306 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 4.10GPa；
336 DEG C of (T of high temperatureg+ 10 DEG C) rubbery state when storage modulus be 2.08GPa.In addition, high-modulus shape note prepared by embodiment five
Recalling composite polyimide material also has preferable shape-memory properties, shape fixed rate 95%, shape recovery rate 82%.
Embodiment six：A kind of preparation method of high-modulus shape memory composite polyimide material is to complete according to the following steps
's：
One, 0.047mol 2- (4- aminophenyls) -5- ammonia base the third oxazoles of benzene are added to 150mL N, N- dimethyl formyls
It in amine, then stirs under the nitrogen atmosphere of room gently dried and is completely dissolved to 2- (4- aminophenyls) -5- ammonia base the third oxazoles of benzene, obtain
To diamine solution；
Two, 0.05mol Bisphenol A Type Diether Dianhydrides are added in the diamine solution obtained in step 1, then in room temperature and
Polymerisation 20h under nitrogen atmosphere, obtains polyamic acid；
Three, gained polyamic acid is poured into container, then carbon cloth is put into wherein, is impregnated 30 hours；
Four, it will be placed on clean glass plate, be subsequently placed in baking oven immersed with the carbon cloth of polyamic acid, then will
Baking oven, from room temperature to 80 DEG C, then keeps the temperature 2h with the heating rate of 1 DEG C/min at being 80 DEG C in temperature, then with 2 DEG C/min's
Heating rate is warming up to 160 DEG C from 80 DEG C, then 2h is kept the temperature at being 160 DEG C in temperature, then with the heating rate of 2 DEG C/min from 160
190 DEG C DEG C are warming up to, then 2h is kept the temperature at being 190 DEG C in temperature, then 250 are warming up to from 190 DEG C with the heating rate of 2 DEG C/min
DEG C, then be 250 DEG C in temperature and keep the temperature 1h, then 300 DEG C are warming up to from 250 DEG C with the heating rate of 1 DEG C/min, then be in temperature
300 DEG C of heat preservation 2h, complete hot-imide, obtain the glass plate containing high-modulus shape memory composite polyimide material；
Five, the glass plate containing high-modulus shape memory composite polyimide material is placed in water, makes high-modulus shape
Memory composite polyimide material film falls off from glass plate, reuses distilled water and rinses film well, then is in temperature
Dry 1h, obtains high-modulus shape memory composite polyimide material at 130 DEG C.
The T of high-modulus shape memory composite polyimide material prepared by embodiment sixgIt is 336 DEG C, ensure that embodiment
The six high-modulus shape memory composite polyimide materials prepared can be applied to high-temperature shape-memory field；Prepared by embodiment six
High-modulus shape memory composite polyimide material is in 316 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 3.91GPa；
346 DEG C of (T of high temperatureg+ 10 DEG C) rubbery state when storage modulus be 1.95GPa.In addition, high-modulus shape note prepared by embodiment six
Recalling composite polyimide material also has preferable shape-memory properties, shape fixed rate 97%, shape recovery rate 83%.
Claims (10)
1. a kind of high-modulus shape memory composite polyimide material, it is characterised in that it is by shape memory polyimides and carbon
Fiber cloth at；The shape memory polyimides is made of diamines and dianhydride；The diamines is 2- (4- aminophenyls)-
5- An base Ben Bing oxazoles；The dianhydride is Bisphenol A Type Diether Dianhydride.
2. a kind of high-modulus shape memory composite polyimide material according to claim 1, it is characterised in that dianhydride：Two
The ratio between amount of substance of amine is 0.90:1~1.10:1.
3. a kind of preparation method of high-modulus shape memory composite polyimide material, it is characterised in that it is complete according to the following steps
At：
One, diamines is added in aprotic polar solvent, then stirring is complete to diamines under the nitrogen atmosphere of room gently dried
Dissolving, obtains diamine solution；
The amount of the diamines substance and the volume ratio of aprotic polar solvent are 0.05mol:(100mL~200mL)；
Two, dianhydride is added in diamine solution, then under conditions of room temperature and mixing speed are 300r/min~800r/min
Polymerisation 5h~30h, obtains polyamic acid solution；
The molar ratio of the dianhydride and diamines is 0.90:1~1.10:1；
Three, carbon cloth is added to immersion 4h~60h in polyamic acid solution, obtains the fiber cloth for being impregnated with polyamic acid；
Four, it will be placed on clean glass plate, be subsequently placed in baking oven, then to baking oven immersed with the carbon cloth of polyamic acid
Temperature programming is carried out, hot-imide is completed, obtains high-modulus shape memory composite polyimide material；
Wherein, the condition of baking oven temperature programming is：
With the heating rate of 1 DEG C/min~2 DEG C/min from room temperature to 70 DEG C~90 DEG C, then 2h is kept the temperature at 70 DEG C~90 DEG C
~3h；
Be warming up to 150 DEG C~170 DEG C from 70 DEG C~90 DEG C again with the heating rate of 1 DEG C/min~2 DEG C/min, then 150 DEG C~
2h~3h is kept the temperature at 170 DEG C；
190 DEG C~210 DEG C are warming up to from 150 DEG C~170 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, then at 190 DEG C
2h~3h is kept the temperature at~210 DEG C；
240 DEG C~260 DEG C are warming up to from 190 DEG C~210 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, then at 240 DEG C
~260 DEG C of heat preservation 1h~2h；
280 DEG C~300 DEG C are warming up to from 240 DEG C~260 DEG C with the heating rate of 1 DEG C/min~2 DEG C/min again, then at 280 DEG C
~300 DEG C of heat preservation 1h~2h；
Room temperature is cooled to from 280 DEG C~300 DEG C with the rate of temperature fall of 1 DEG C/min~2 DEG C/min again；
Five, the glass plate containing high-modulus shape memory composite polyimide material is placed in distilled water, keeps shape memory poly-
Acid imide composite material falls off from glass plate, reuses distilled water and is rinsed well, then is dried at being 120 DEG C in temperature
3h obtains high-modulus shape memory composite polyimide material；
The diamines is 2- (4- aminophenyls) -5- An base Ben Bing oxazoles；Dianhydride is Bisphenol A Type Diether Dianhydride.
4. a kind of preparation method of high-modulus shape memory composite polyimide material according to claim 3, feature
It is that the aprotic polar solvent described in step 1 is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N- methyl pyrroles
Pyrrolidone.
5. a kind of preparation method of high-modulus shape memory composite polyimide material according to claim 3, feature
The volume ratio of the amount and aprotic polar solvent that are the diamines substance described in step 1 is 0.05mol:(100mL~
180mL)。
6. a kind of preparation method of high-modulus shape memory composite polyimide material according to claim 3, feature
The volume ratio of the amount and aprotic polar solvent that are the diamines substance described in step 1 is 0.05mol:(100mL~
190mL)。
7. a kind of preparation method of high-modulus shape memory composite polyimide material according to claim 3, feature
It is that the molar ratio of the dianhydride and diamines described in step 2 is 0.90:1~1.0:1.
8. a kind of preparation method of high-modulus shape memory composite polyimide material according to claim 3, feature
It is that step 3 kind carbon cloth impregnates 10h~60h in polyamic acid solution.
9. a kind of preparation method of high-modulus shape memory composite polyimide material according to claim 3, feature
It is that the condition of baking oven temperature programming in step 4 is：
With the heating rate of 1 DEG C/min from room temperature to 80 DEG C, then 2h is kept the temperature at 80 DEG C；
It is warming up to 160 DEG C from 80 DEG C with the heating rate of 2 DEG C/min again, then 2h is kept the temperature at 160 DEG C；
It is warming up to 190 DEG C from 160 DEG C with the heating rate of 1 DEG C/min again, then 2h is kept the temperature at 190 DEG C；
It is warming up to 250 DEG C from 190 DEG C with the heating rate of 1 DEG C/min again, then keeps the temperature 1h at 250 DEG C；
It is warming up to 280 DEG C from 260 DEG C with the heating rate of 1 DEG C/min again, then keeps the temperature 1h at 280 DEG C；
Room temperature is cooled to from 280 DEG C~300 DEG C with the rate of temperature fall of 1 DEG C/min~2 DEG C/min again.
10. a kind of preparation method of high-modulus shape memory composite polyimide material according to claim 3, feature
It is that the condition of baking oven temperature programming in step 4 is：
With the heating rate of 1 DEG C/min from room temperature to 80 DEG C, then 2h is kept the temperature at 80 DEG C；
It is warming up to 160 DEG C from 80 DEG C with the heating rate of 2 DEG C/min again, then 2h is kept the temperature at 160 DEG C；
It is warming up to 190 DEG C from 160 DEG C with the heating rate of 1 DEG C/min again, then 2h is kept the temperature at 190 DEG C；
It is warming up to 250 DEG C from 190 DEG C with the heating rate of 1 DEG C/min again, then keeps the temperature 1h at 250 DEG C；
It is warming up to 280 DEG C from 260 DEG C with the heating rate of 1 DEG C/min again, then keeps the temperature 1h at 280 DEG C,
Room temperature is cooled to from 280 DEG C~300 DEG C with the rate of temperature fall of 1 DEG C/min~2 DEG C/min again.
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| CN109651611A (en) * | 2018-12-29 | 2019-04-19 | 哈尔滨工业大学 | A kind of shape memory polyimides prepreg, composite material and preparation method |
| CN111303425A (en) * | 2020-04-20 | 2020-06-19 | 中国科学院兰州化学物理研究所 | Photo-thermal response three-dimensional shape memory polyimide and preparation method and application thereof |
| CN114889235A (en) * | 2022-05-24 | 2022-08-12 | 哈尔滨工业大学 | Pearl shell structure-imitated SMPI fire-resistant flame-retardant material and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651611A (en) * | 2018-12-29 | 2019-04-19 | 哈尔滨工业大学 | A kind of shape memory polyimides prepreg, composite material and preparation method |
| CN111303425A (en) * | 2020-04-20 | 2020-06-19 | 中国科学院兰州化学物理研究所 | Photo-thermal response three-dimensional shape memory polyimide and preparation method and application thereof |
| CN114889235A (en) * | 2022-05-24 | 2022-08-12 | 哈尔滨工业大学 | Pearl shell structure-imitated SMPI fire-resistant flame-retardant material and preparation method and application thereof |
| CN114889235B (en) * | 2022-05-24 | 2024-01-26 | 哈尔滨工业大学 | SMAI (styrene-butadiene-styrene) fireproof flame-retardant material with mother-of-pearl structure, and preparation method and application thereof |
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