CN108117749A - The preparation method of polyimides/sisal cellulose crystallite composite material of shape memory - Google Patents
The preparation method of polyimides/sisal cellulose crystallite composite material of shape memory Download PDFInfo
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- CN108117749A CN108117749A CN201711413711.1A CN201711413711A CN108117749A CN 108117749 A CN108117749 A CN 108117749A CN 201711413711 A CN201711413711 A CN 201711413711A CN 108117749 A CN108117749 A CN 108117749A
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- Prior art keywords
- sisal cellulose
- cellulose crystallite
- sisal
- polyimides
- baking oven
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- 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
- 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
-
- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
- C08J2401/04—Oxycellulose; Hydrocellulose
Abstract
The invention discloses a kind of preparation methods of polyimides/sisal cellulose crystallite composite material of shape memory.Sisal cellulose crystallite is placed in baking oven at 100 DEG C dry 2 ~ 4 h, dried sisal cellulose crystallite is made, then with ODA, ODPA and NMP mixing is added in three-necked flask, under nitrogen atmosphere 24 h are stirred to react in 25 DEG C, the sticky PAA solution containing sisal cellulose crystallite is made, 30 min of ultrasonic disperse, PAA solution containing sisal cellulose crystallite is uniformly applied on horizontal mold, then mold is put into baking oven and carries out hot imidization reaction, after reaction, baking oven cooled to room temperature, take out mold, thin film separation is come out, as polyimides/sisal cellulose crystallite composite material.The method of the present invention is easy to operate, application easy to promote large-scale, and polyimides obtained/sisal cellulose crystallite composite material has excellent stretch modulus, heat resistance, and with certain shape-memory properties.
Description
Technical field
The invention belongs to intelligent composite technical field, more particularly to a kind of polyimides/sisal cellulose crystallite shape
The preparation method of shape memory composite material.
Background technology
The shape memory switch temperature of traditional shape-memory polymer is generally lower than 150 DEG C, which has limited it in work
Application in journey, the application especially in aerospace industries.In order to meet shape-memory polymer in severe rugged environment（Such as height
Temperature, space radiation etc.）Under application requirement, in recent years shape-memory polymer constantly become research hotspot, wherein most typical
Representative is exactly polyimides（PI）.There is PI excellent thermal stability, chemical stability, electric insulating quality, high-vitrification to turn
The series of advantages such as temperature, high mechanical properties and radiation hardness.Sisal cellulose crystallite has the characteristics such as environmentally friendly, degradable, and
And largely exist in nature, belong to Guangxi characteristic renewable resource, adaptation to local conditions.We introduce sisal hemp in polyimides
Cellulose crystallite prepares composite polyimide material, is equivalent to and other active forces are introduced in system, further improve material
Shape-memory properties.
We select to use the sisal cellulose crystallite of natural surroundings close friend compound as polyimides in the present patent application
The filler of material takes full advantage of the special crop of this area, to widen the application field of sisal cellulose crystallite, supports local
The development utilization of advantage characteristic natural resources, and take full advantage of the effect of the collaboration on sisal cellulose crystallite and polyimides performance
Should, while widened the application field of sisal cellulose crystallite and polyimides.This thinking has no document report.
The content of the invention
The object of the present invention is to provide a kind of preparation sides of polyimides/sisal cellulose crystallite composite material of shape memory
Method.
It concretely comprises the following steps：
(1) sisal cellulose crystallite is placed in baking oven at 100 DEG C dry 2 ~ 4 h, it is micro- that dried sisal cellulose is made
It is brilliant.
(2) ODA of 0.0025 mol is weighed, is added in three-necked flask, clean small magnetite is added in, reinjects 10 mL's
NMP, open magnetic stirring apparatus, adjustment velocity of rotation be 200 ~ 400 revs/min, then add in 0.0025 mol ODPA and
Dried sisal cellulose crystallite made from step (1), the entire process for adding in raw materials and reagents are completed in 15 min, so
24 h are stirred to react in 25 DEG C under nitrogen atmosphere afterwards, the sticky PAA solution containing sisal cellulose crystallite is made；It is described dry
The dosage of sisal cellulose crystallite after dry is ODA and the 1 ~ 2% of ODPA gross masses.
(3) by 30 min of PAA solution ultrasonic disperse containing sisal cellulose crystallite made from step (2), ultrasonic disperse
After, the PAA solution containing sisal cellulose crystallite is uniformly applied on horizontal mold, mold is then put into baking
Case carries out hot imidization reaction, and the temperature program for setting baking oven is temperature-gradient method pattern：The first step, 70 DEG C of 4 h of holding；Second
Step is warming up to 100 DEG C of 1 h of holding；3rd step is warming up to 200 DEG C of 1 h of holding；4th step is warming up to 300 DEG C of 1 h of holding,
After heating, baking oven cooled to room temperature is taken out mold, thin film separation is come out, gained film is polyimides/sword
Flaxen fiber element crystallite composite material.
The method of the present invention is easy to operate, application easy to promote large-scale, and takes full advantage of sisal cellulose crystallite and gather
Mutual supplement with each other's advantages of the acid imide in performance makes polyimides obtained/sisal cellulose crystallite composite material have excellent drawing
Modulus, heat resistance are stretched, and with certain shape-memory properties, there is important application prospect in fields such as aerospaces.
Description of the drawings
Fig. 1 is the SEM photograph of polyimides obtained/sisal cellulose crystallite composite material in the embodiment of the present invention 2.
Specific embodiment
Compare example：
(1) sisal cellulose crystallite is placed in baking oven at 100 DEG C dry 3 h, it is micro- that dried sisal cellulose is made
It is brilliant.
(2) ODA of 0.0025 mol is weighed, is added in three-necked flask, clean small magnetite is added in, reinjects 10 mL's
NMP opens magnetic stirring apparatus, and adjustment velocity of rotation is 300 revs/min, then adds in the ODPA of 0.0025 mol, entire to add in
The process of raw materials and reagents is completed in 15 min, is then stirred to react 24 h in 25 DEG C under nitrogen atmosphere, is made sticky
PAA solution.
(3) PAA solution made from step (2) is uniformly applied on horizontal mold, mold is then put into baking oven
Hot imidization reaction is carried out, the temperature program for setting baking oven is temperature-gradient method pattern：The first step, 70 DEG C of 4 h of holding；Second step,
It is warming up to 100 DEG C of 1 h of holding；3rd step is warming up to 200 DEG C of 1 h of holding；4th step is warming up to 300 DEG C of 1 h of holding, rises
After temperature, baking oven cooled to room temperature is taken out mold, thin film separation is come out, gained film is polyimide material.
Embodiment 1：
(1) sisal cellulose crystallite is placed in baking oven at 100 DEG C dry 3 h, it is micro- that dried sisal cellulose is made
It is brilliant.
(2) ODA of 0.0025 mol is weighed, is added in three-necked flask, clean small magnetite is added in, reinjects 10 mL's
NMP opens magnetic stirring apparatus, and adjustment velocity of rotation is 300 revs/min, then adds in the ODPA and step of 0.0025 mol
(1) dried sisal cellulose crystallite made from, the entire process for adding in raw materials and reagents are completed in 15 min, Ran Hou
24 h are stirred to react in 25 DEG C under blanket of nitrogen, the sticky PAA solution containing sisal cellulose crystallite is made；After the drying
The dosage of sisal cellulose crystallite be the 1% of ODA and ODPA gross masses.
(3) by 30 min of PAA solution ultrasonic disperse containing sisal cellulose crystallite made from step (2), ultrasonic disperse
After, the PAA solution containing sisal cellulose crystallite is uniformly applied on horizontal mold, mold is then put into baking
Case carries out hot imidization reaction, and the temperature program for setting baking oven is temperature-gradient method pattern：The first step, 70 DEG C of 4 h of holding；Second
Step is warming up to 100 DEG C of 1 h of holding；3rd step is warming up to 200 DEG C of 1 h of holding；4th step is warming up to 300 DEG C of 1 h of holding,
After heating, baking oven cooled to room temperature is taken out mold, thin film separation is come out, gained film is polyimides/sword
Flaxen fiber element crystallite composite material.
Embodiment 2：
(1) sisal cellulose crystallite is placed in baking oven at 100 DEG C dry 3 h, it is micro- that dried sisal cellulose is made
It is brilliant.
(2) ODA of 0.0025 mol is weighed, is added in three-necked flask, clean small magnetite is added in, reinjects 10 mL's
NMP opens magnetic stirring apparatus, and adjustment velocity of rotation is 300 revs/min, then adds in the ODPA and step of 0.0025 mol
(1) dried sisal cellulose crystallite made from, the entire process for adding in raw materials and reagents are completed in 15 min, Ran Hou
24 h are stirred to react in 25 DEG C under blanket of nitrogen, the sticky PAA solution containing sisal cellulose crystallite is made；After the drying
The dosage of sisal cellulose crystallite be the 1.5% of ODA and ODPA gross masses.
(3) by 30 min of PAA solution ultrasonic disperse containing sisal cellulose crystallite made from step (2), ultrasonic disperse
After, the PAA solution containing sisal cellulose crystallite is uniformly applied on horizontal mold, mold is then put into baking
Case carries out hot imidization reaction, and the temperature program for setting baking oven is temperature-gradient method pattern：The first step, 70 DEG C of 4 h of holding；Second
Step is warming up to 100 DEG C of 1 h of holding；3rd step is warming up to 200 DEG C of 1 h of holding；4th step is warming up to 300 DEG C of 1 h of holding,
After heating, baking oven cooled to room temperature is taken out mold, thin film separation is come out, gained film is polyimides/sword
Flaxen fiber element crystallite composite material.
Embodiment 3：
(1) sisal cellulose crystallite is placed in baking oven at 100 DEG C dry 3 h, it is micro- that dried sisal cellulose is made
It is brilliant.
(2) ODA of 0.0025 mol is weighed, is added in three-necked flask, clean small magnetite is added in, reinjects 10 mL's
NMP opens magnetic stirring apparatus, and adjustment velocity of rotation is 300 revs/min, then adds in the ODPA and step of 0.0025 mol
(1) dried sisal cellulose crystallite made from, the entire process for adding in raw materials and reagents are completed in 15 min, Ran Hou
24 h are stirred to react in 25 DEG C under blanket of nitrogen, the sticky PAA solution containing sisal cellulose crystallite is made；After the drying
The dosage of sisal cellulose crystallite be the 2% of ODA and ODPA gross masses.
(3) by 30 min of PAA solution ultrasonic disperse containing sisal cellulose crystallite made from step (2), ultrasonic disperse
After, the PAA solution containing sisal cellulose crystallite is uniformly applied on horizontal mold, mold is then put into baking
Case carries out hot imidization reaction, and the temperature program for setting baking oven is temperature-gradient method pattern：The first step, 70 DEG C of 4 h of holding；Second
Step is warming up to 100 DEG C of 1 h of holding；3rd step is warming up to 200 DEG C of 1 h of holding；4th step is warming up to 300 DEG C of 1 h of holding,
After heating, baking oven cooled to room temperature is taken out mold, thin film separation is come out, gained film is polyimides/sword
Flaxen fiber element crystallite composite material.
By polyimides made from embodiment 1 ~ 3/sisal cellulose crystallite composite material and compare polyamides Asia made from example
Amine material carries out performance comparison, and the stretch modulus highest of polyimides/sisal cellulose crystallite composite material is improved to 1428.7
MPa, than not plus sisal cellulose crystallite improves 128.89%；In addition, polyimides/sisal cellulose crystallite composite material
Excellent heat resistance, 805 DEG C of carbon yield is more than 40%, half longevity decomposition temperature Td50%It is above 600 DEG C；Finally, polyamides
Imines/sisal cellulose crystallite composite material shows obtained poly- in certain shape-memory properties, especially embodiment 1
Shape fixed rate and shape recovery rate after the succeeding stretch Xun Huan of acid imide/sisal cellulose crystallite composite material are above
More than 90%.
Claims (1)
- A kind of 1. preparation method of polyimides/sisal cellulose crystallite composite material of shape memory, it is characterised in that specific step Suddenly it is：(1) sisal cellulose crystallite is placed in baking oven at 100 DEG C dry 2 ~ 4 h, it is micro- that dried sisal cellulose is made It is brilliant；(2) ODA of 0.0025 mol is weighed, is added in three-necked flask, adds in clean small magnetite, reinjects the NMP of 10 mL, Magnetic stirring apparatus is opened, adjustment velocity of rotation is 200 ~ 400 revs/min, then adds in the ODPA and step of 0.0025 mol (1) dried sisal cellulose crystallite made from, the entire process for adding in raw materials and reagents are completed in 15 min, Ran Hou 24 h are stirred to react in 25 DEG C under blanket of nitrogen, the sticky PAA solution containing sisal cellulose crystallite is made；After the drying The dosage of sisal cellulose crystallite be the 1 ~ 2% of ODA and ODPA gross masses；(3) by 30 min of PAA solution ultrasonic disperse containing sisal cellulose crystallite made from step (2), ultrasonic disperse terminates Afterwards, the PAA solution containing sisal cellulose crystallite is uniformly applied on horizontal mold, then by mold be put into baking oven into Row hot imidization reacts, and the temperature program for setting baking oven is temperature-gradient method pattern：The first step, 70 DEG C of 4 h of holding；Second step rises Temperature to 100 DEG C holding 1 h；3rd step is warming up to 200 DEG C of 1 h of holding；4th step is warming up to 300 DEG C of 1 h of holding, heating After, baking oven cooled to room temperature takes out mold, thin film separation is come out, and gained film is that polyimides/sisal hemp is fine The plain crystallite composite material of dimension.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040449A (en) * | 2019-12-26 | 2020-04-21 | 合肥中汇睿能能源科技有限公司 | Modified polyimide film and preparation method thereof |
| CN111171568A (en) * | 2020-03-07 | 2020-05-19 | 桂林理工大学 | Preparation method of fluorine-containing and sulfone-containing polyimide-based friction material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040449A (en) * | 2019-12-26 | 2020-04-21 | 合肥中汇睿能能源科技有限公司 | Modified polyimide film and preparation method thereof |
| CN111171568A (en) * | 2020-03-07 | 2020-05-19 | 桂林理工大学 | Preparation method of fluorine-containing and sulfone-containing polyimide-based friction material |
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Application publication date: 20180605 |