CN105254888B - Polyimides ionomer and preparation method thereof - Google Patents
Polyimides ionomer and preparation method thereof Download PDFInfo
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- CN105254888B CN105254888B CN201510815178.6A CN201510815178A CN105254888B CN 105254888 B CN105254888 B CN 105254888B CN 201510815178 A CN201510815178 A CN 201510815178A CN 105254888 B CN105254888 B CN 105254888B
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Abstract
The present invention discloses a kind of preparation method of polyimides ionomer, comprising: at 0-25 DEG C, under the conditions of inert gas shielding, diamines is dissolved in solvent by lasting stirring；The dianhydride for weighing equimolar amounts is added portionwise, and adds solvent, continues to stir, and obtains the higher polyamic acid solution of viscosity；Calcium hydroxide particle is added in polyamic acid solution, reaction is futher stirred, obtains the polyamic acid salting liquid of homogeneous transparent；Polyamic acid salting liquid is laid on substrate, it is dry to remove solvent, then polyimides ionomer films are obtained by substep heating hot imidization.The present invention also provides a kind of polyimides ionomers obtained by the above method.The polyimides ionomer has high-temperature shape-memory characteristic.
Description
Technical field
The present invention relates to a kind of polyimides ionomer and preparation method thereof, in particular to a kind of high temperature of calcium ion crosslinking
Shape memory polyimides ionomer and preparation method thereof.
Background technique
Shape-memory material refers to the variation that shape can occur under extraneous conditional stimulus, and keeps under certain condition
The temporary deformation, and a kind of material of original-shape can be returned to when incentive condition applies again.With marmem
It is compared with shape memory ceramics, shape-memory polymer (SMP) has density low, and deformation quantity is big, and at low cost, processing preparation is simple
It waits many merits and is concerned.Based on these advantages, SMP is in biomedical devices, intelligent textile material, intelligence sensor,
The numerous areas such as aviation and wide have broad application prospects.
The shape memory characteristic of SMP derives from its special two phase structure: can anti-phase and stationary phase.Reversible phase is turned by phase
The fixed temporary shapes of phase-state change during change, can be crystallization-melting transition or the unformed transformation of glassy state-.Stationary phase
Play a part of memory material original-shape, can be physical crosslinking point or chemical crosslinking point.The SMP material studied at present
Mainly have polyurethane, polyolefin, epoxy resin, polyacrylate etc. [Progress in Polymer Science, 2012,37
(12):1720-1763].Voit etc. reports a kind of heat curing type polymethacrylate copolymer, the reversible recovery strain of highest
Up to 800% [Advanced Functional Materials, 2010,20 (1): 162-171].Shandas etc. then uses light
The method of crosslinking is prepared for a kind of biocompatibility SMP material, has studied its application in angiocarpy bracket
[Biomaterials, 2007,28 (14): 2255-2263].Zhang etc. is then prepared for a kind of polylactic acid-carbonic ester shape memory
Copolymer, have studied its in bionic fiber bracket application [ACS Applied Materials&Interfaces, 6 (4):
2611-2621]。
By MOLECULE DESIGN appropriate, although above-mentioned polymer material can embody higher shape-memory properties,
But there is also some disadvantages, such as lower mechanical strength, response temperature (being lower than 150 DEG C) and restoring force etc..These defects
Limit application of these materials in some more harsh environments, such as hot environment, space environment.Therefore, one is prepared
It is when previous important research topic that kind, which has high-intensitive high temperature SMP,.
Polyimides refers to the quasi polymer for containing imide ring (- CO-NH-CO-) on main chain, wherein to contain phthaloyl
The polymer of imine structure is mostly important.Polyimides has high temperature resistant, radiation hardness, mechanical performance excellent etc. a little, as one
The special engineered material of kind, has been widely used in fields such as Aeronautics and Astronautics, microelectronics, nanometer, liquid crystal, seperation film, laser.But not
Specially designed polyimides can not embody shape memory characteristic.For this purpose, two phase structure of the present invention according to SMP
Ionization introducing polyimides is prepared a kind of novel ionomers, can embody excellent mechanical strength and shape by mechanism
Memory performance.
Summary of the invention
The present invention provides a kind of preparation method of polyimides ionomer, comprising:
At 0-25 DEG C, under the conditions of inert gas shielding, diamines is dissolved in solvent by lasting stirring；Weigh equimolar amounts
Dianhydride be added portionwise, and add solvent, continue to stir, obtain the higher polyamic acid solution of viscosity；
Calcium hydroxide particle is added in polyamic acid solution, reaction is futher stirred, obtains the polyamide of homogeneous transparent
Acid salt solution；
Polyamic acid salting liquid is laid on substrate, it is dry to remove solvent, then obtained by substep heating hot imidization
To polyimides ionomer films.
Further, the time control that the dianhydride for weighing equimolar amounts is added portionwise adds in 15-30min minutes
It is complete.
Further, the diamines is selected from 4,4'- diaminodiphenyl ether, 3,4'- diaminodiphenyl ethers, 4,4 '-diamino
Diphenyl methane, bis- (4- amino-benzene oxygen) benzene of Isosorbide-5-Nitrae -, bis- (4- amino-benzene oxygen) methane, 4,4'- diamino -3,3'- diformazans
Base biphenyl, 3,3'- dimethyl -4,4'- benzidines, 3,3 '-dimethyl -4,4 '-diaminodiphenyl-methanes, 1,1- is bis-
At least one of (4'- aminophenyl) hexamethylene.
Further, the dianhydride be selected from 3,3', 4,4'- diphenyl ether tetracid dianhydrides, 3,3', 4,4'- biphenyltetracarboxylic dianhydride,
4,4'(to benzene) two ether dianhydrides, 3,3', 4,4'- benzophenone tetracarboxylic dianhydrides, bis- (3,4- dicarboxyphenyi) methane dianhydrides, 2,
At least one of bis- (bis- carboxy phenyl of 3,4-) hexafluoropropane tetracid dianhydrides of 2'-.
Further, the solvent is selected from toluene, n,N-dimethylacetamide, and at least one in N-Methyl pyrrolidone
Kind.
Further, when the solvent is toluene, drying temperature is 50-70 DEG C；When solvent is N, N- dimethylacetamide
When amine, drying temperature is 70-90 DEG C；When solvent is N-Methyl pyrrolidone, drying temperature is 70-90 DEG C.
Further, solid content is controlled in 8-16wt% in the polyamic acid solution.
Further, the partial size of the calcium hydroxide particle is 1-50 μm.
Further, the step of substep heats up are as follows:
1h at 100 DEG C, 1h at 150 DEG C, 1h at 200 DEG C, 1h at 250 DEG C, 1h at 300 DEG C；Or 1h at 100 DEG C, at 200 DEG C
1h, 2h at 300 DEG C.
The present invention furthermore provides one kind and obtains a kind of polyimides ionomer by the above method.
Polyimides ionomer provided by the invention and preparation method thereof, has the advantage that
1. calcium ion crosslinking is acted on by relatively simple method and introduces polyimides network by the present invention, it is prepared for one kind
The introducing of new type polyimide ionomer, ionomer effect can be improved the mechanical property of material, while be made with ionomer
It is used as stationary phase, material has excellent shape-memory properties.
2. the glass transition temperature of polyimides ionomer of the invention, can be real at high temperature up to 270 DEG C or more
Existing shape-memory properties overcome defect of the currently used SMP compared with low-response temperature (mostly lower than 150 DEG C), ensure that it
It can be applied to the intellectual material of high-temperature field.
3. the storage modulu of polyimides ionomer of the invention in room temperature (25 DEG C) glassy state is up to 2.8GPa or more,
It can guarantee the size and shape stability of component when using as structural material.
4. polyimides ionomer of the invention, up to 35MPa or more, is guaranteeing to possess in high temperature (300 DEG C) rubbery state
While higher shape fixed rate, recovery of shape power and recovery of shape speed also with higher, 180 DEG C of curved shapes are replied
Time only needs 5-15s.
5. preparation method of the invention also has the features such as simple process, easy to industrialized production.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of polyimides ionomer provided in an embodiment of the present invention.
Fig. 2 is the structural schematic diagram of polyimides ionomer provided in an embodiment of the present invention.
Fig. 3 is the stereoscan photograph of polyimides ionomer provided in an embodiment of the present invention.
Fig. 4 is the loss modulus curve (tan δ) and storage modulu song of polyimides ionomer provided in an embodiment of the present invention
Line (E ').
Fig. 5 is the memory cycle curve of polyimides ionomer provided in an embodiment of the present invention.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.It is understood that this place is retouched
State that the specific embodiments are only for explaining the present invention, rather than limitation of the invention.It also should be noted that for the ease of
It describes, only the parts related to the present invention are shown rather than entire infrastructure in attached drawing.
Fig. 1 is please referred to, the embodiment of the present invention provides a kind of preparation method of polyimides ionomer, comprising:
S1, at 0-25 DEG C, under the conditions of inert gas shielding, diamines is dissolved in solvent by lasting stirring；It weighs etc. and to rub
You are added portionwise the dianhydride of amount, and add solvent and continue to stir, and obtain the higher polyamic acid solution of viscosity；
Calcium hydroxide particle is added in polyamic acid solution, futher stirs reaction, obtain the polyamides of homogeneous transparent by S2
Amino acid salting liquid；And
Polyamic acid salting liquid is laid on substrate by S3, dry to remove solvent, then passes through substep heating hot imidization
Obtain polyimides ionomer films.
In step sl, the inert gas can be rare gas, nitrogen etc..Diamines is dissolved in by the lasting stirring
The mixing time of solvent is 30-60min.The time control that the dianhydride for weighing equimolar amounts is added portionwise is at 15-30min points
It is added in clock.The mixing time added solvent and continue stirring is 16-32h.The diamines is selected from 4,4'- diamino hexichol
Ether, 3,4'- diaminodiphenyl ethers, 4,4 '-diaminodiphenyl-methanes, bis- (4- amino-benzene oxygen) benzene of Isosorbide-5-Nitrae-, bis- (4- aminobenzenes
Oxygroup) methane, 4,4'- diamino -3,3'- dimethyl diphenyls, 3,3'- dimethyl -4,4'- benzidines, 3,3 '-diformazans
4,4 '-diaminodiphenyl-methane of base-, at least one of 1,1- bis- (4'- aminophenyl) hexamethylenes.The dianhydride is selected from 3,
3', 4,4'- diphenyl ether tetracid dianhydrides, 3,3', 4,4'- biphenyltetracarboxylic dianhydride, 4,4'(to benzene) two ether dianhydrides, 3,3', 4,4'- bis-
Benzophenone tetracarboxylic acid dianhydride, bis- (3,4- dicarboxyphenyi) methane dianhydrides, 2,2'- bis- (3,4- bis- carboxy phenyl) hexafluoropropane tetracids
At least one of dianhydride.The solvent is selected from toluene, n,N-dimethylacetamide, and at least one in N-Methyl pyrrolidone
Kind.Solid content control is in 8-16wt% in the polyamic acid solution, to obtain higher viscosity.
In step s 2, the partial size of the calcium hydroxide particle is 1-50 μm.Preferably, the grain of the calcium hydroxide particle
Diameter is 10-30 μm.It is furthermore preferred that the partial size of the calcium hydroxide particle is 20-30 μm.It is appreciated that different content is added
Calcium hydroxide particle, the ionomer degree of adjustable prepared ionomer.It is described to futher stir reaction, obtain homogeneous transparent
Polyamic acid salting liquid mixing time be 48-120h.
In step s3, it is described by polyamic acid salting liquid be laid on substrate with a thickness of 10 μm -500 μm.It is described dry
Dry temperature is 50-90 DEG C, drying time 3-6h.It is demonstrated experimentally that it is suitable to need to select according to the difference of selected solvent
Drying temperature is subject to and controls evaporation rate and bubble is avoided to generate.When the solvent is toluene, drying temperature is preferably
50-70℃；When solvent is n,N-dimethylacetamide, drying temperature is preferably 70-90 DEG C；When solvent is N- crassitude
When ketone, drying temperature is preferably 70-90 DEG C.Further, the step of substep heats up are as follows:
1) 1h at 100 DEG C, 1h at 150 DEG C, 1h at 200 DEG C, 1h at 250 DEG C, 1h at 300 DEG C；Or
2) 1h at 100 DEG C, 1h at 200 DEG C, 2h at 300 DEG C.
The present invention furthermore provides one kind and obtains a kind of polyimides ionomer by the above method.
Embodiment 1
In the N- methyl under room temperature, weighing 2.0g (0.01mol) 4,4'- diaminodiphenyl ether (ODA) and being dissolved in 25mL
In pyrrolidones, 30min is persistently stirred under N2 protection.Weigh 3.1g (0.01mol) 3,3', 4,4'- diphenyl ether tetracid dianhydride
(ODPA), the above solution is added in batches, while adding the N-Methyl pyrrolidone of 25mL by several times, in being added in 20min, into one
Step reaction obtains sticky polyamic acid solution for 24 hours.It weighs 0.037g (0.5mmol) calcium hydroxide and polyamic acid solution is added
In, polyamic acid salting liquid is obtained until solution is become clarifying completely from muddiness in lower the reaction was continued the 72h of N2 protection.By gained
Solution is laid on glass plate, prior to 80 DEG C dry 4h, then carries out hot imidization, and specific temperature-rise period is 1h at 100 DEG C,
1h at 200 DEG C, 2h at 300 DEG C.Finally obtain the polyimides ionomer films with a thickness of 50-200 μm.
Referring to figure 2. -3, the characterization of polyimides ionomer and shape-memory properties test: using scanning electron microscopic observation from
Polymers cross-section morphology, Latitudinal section many nanoscales protrusion and pit, show the enhancing to material of ionomer point
Effect；The infrared spectroscopy of bond material shows calcium hydroxide in the complete reacting forming ion cross-linked network of polyamic acid.From poly-
The glass transition temperature of object is its recovery of shape temperature, closely related with its chain movement ability.Material is improved under normal circumstances
The degree of cross linking can reduce the locomitivity of polymer chain, to improve its glass transition temperature.It is analyzed using dynamic thermomechanical
Instrument (DMA) measures the loss modulus curve (tan δ) and storage modulu curve (E ') of material, obtains material by loss modulus peak
Glass transition temperature.DMA experiment is to be carried out with stretch mode using DMA 242C, experiment parameter are as follows: constant frequency 1Hz, most
60 μm of large amplitude, 5 DEG C of min of the rate of heat addition-1.The introducing of ionomer point, makes the glass of ionomer it can be seen from attached drawing 4
Change transition temperature and is increased to 274.0 DEG C by 260.7 DEG C of PI.The material it can be seen from the storage modulu curve of attached drawing 4 simultaneously
Storage modulu positioned at elastomeric state improves 34.9MPa by the 15.0MPa of PI, shows that the restoring force of material and reply speed all obtain
It is obviously improved.
The shape-memory properties test of material is equally carried out using DMA, cyclic tension program used are as follows: be by initial strain
ε0Sample is heated to 325 DEG C and applies a constant external force, and reduction temperature to 20 DEG C of holding 5min obtains maximum strain εm；It removes
External force simultaneously keeps 5min to obtain temporary strian εu；Again 325 DEG C are warming up to, and 1h is kept to obtain recovery strain εp.Hereafter continue weight
This multiple circulation.Attached drawing 5 gives the memory cycle curve an of ionomer.Shape fixed rate (Rf) and shape recovery rate
(Rr) formula it is as follows:
Rf=(εu-ε0)/(εm-ε0)
Rr=(εu-εp)/(εu-ε0)
Using ionomer point as stationary phase, material has preferable shape-memory properties, shape fixed rate and shape
Response rate can reach 99% and 90% or more respectively.
Embodiment 2
It is substantially the same manner as Example 1, the difference is that, 0.074g (1mmol) calcium hydroxide is added, the reaction was continued
120h, until solution is become clarifying from muddiness.
Transition temperature, shape fixed rate and the shape recovery rate of material are measured as described in Example 1.The vitrifying of material
Transition temperature is 276.8 DEG C, and shape fixed rate and shape recovery rate are respectively up to 99% and 80% or more.
Embodiment 3
It is substantially the same manner as Example 1, the difference is that, select 3,3', 4,4'- biphenyltetracarboxylic dianhydride as dianhydride monomer
It prepares polyamic acid, calcium hydroxide the reaction was continued the 48h of 0.0074g (0.1mmol) is added.
Transition temperature, shape fixed rate and the shape recovery rate of material are measured as described in Example 1.The vitrifying of material
Transition temperature is 275.5 DEG C, and shape fixed rate and shape recovery rate are respectively up to 97% and 93%.
Embodiment 4
It is substantially the same manner as Example 1, the difference is that, select 3,3', 4,4'- biphenyltetracarboxylic dianhydride as dianhydride monomer
Polyamic acid is prepared, 0.037g (0.5mmol) calcium hydroxide reaction 72h is added, obtains polyamic acid salting liquid.
The shape fixed rate and shape recovery rate of material are measured as described in Example 1.The shape fixed rate of material and return
Multiple rate is respectively up to 98% and 90%.
Embodiment 5
It is substantially the same manner as Example 1, the difference is that, 3,4'- diaminodiphenyl ether, which is selected, as diamines prepares polyamides
Amino acid.
The shape fixed rate and shape recovery rate of material are measured as described in Example 1.The shape fixed rate of material and return
Multiple rate is respectively up to 98% and 90%.
Embodiment 6
It is substantially the same manner as Example 1, the difference is that, select bis- (3,4- bis- carboxy phenyl) the hexafluoropropane tetracids of 2,2'-
Dianhydride is that dianhydride prepares polyamic acid.
The shape fixed rate and shape recovery rate of material are measured as described in Example 1.The shape fixed rate of material and return
Multiple rate is respectively up to 97% and 90%.
Note that the above is only a better embodiment of the present invention and the applied technical principle.It will be appreciated by those skilled in the art that
The invention is not limited to the specific embodiments described herein, be able to carry out for a person skilled in the art it is various it is apparent variation,
It readjusts and substitutes without departing from protection scope of the present invention.Therefore, although being carried out by above embodiments to the present invention
It is described in further detail, but the present invention is not limited to the above embodiments only, without departing from the inventive concept, also
It may include more other equivalent embodiments, and the scope of the invention is determined by the scope of the appended claims.
Claims (9)
1. a kind of preparation method of polyimides ionomer, comprising:
At 0-25 DEG C, under the conditions of inert gas shielding, diamines is dissolved in solvent by lasting stirring；Weigh the two of equimolar amounts
Acid anhydride is added portionwise, and adds solvent, continues to stir, and obtains solid content control in the polyamic acid solution of 8-16wt%；
Calcium hydroxide particle is added in polyamic acid solution, reaction 48-72h is futher stirred, obtains the polyamides of homogeneous transparent
Amino acid salting liquid；
Polyamic acid salting liquid is laid on substrate, it is dry to remove solvent, then gathered by substep heating hot imidization
Acid imide ionomer films.
2. the preparation method of polyimides ionomer according to claim 1, which is characterized in that described to weigh equimolar amounts
Dianhydride be added portionwise time control added in 15-30min minutes.
3. the preparation method of polyimides ionomer according to claim 1, which is characterized in that the diamines is selected from 4,
4'- diaminodiphenyl ether, 3,4'- diaminodiphenyl ethers, 4,4 '-diaminodiphenyl-methanes, Isosorbide-5-Nitrae-are bis- (4- amino-benzene oxygen)
Benzene, bis- (4- amino-benzene oxygen) methane, 4,4'- diamino -3,3'- dimethyl diphenyls, 3,3'- dimethyl -4,4'- diamino connection
Benzene, 3,3 '-dimethyl -4,4 '-diaminodiphenyl-methanes, at least one of 1,1- bis- (4'- aminophenyl) hexamethylenes.
4. the preparation method of polyimides ionomer according to claim 1, which is characterized in that the dianhydride is selected from 3,
3', 4,4'- diphenyl ether tetracid dianhydrides, 3,3', 4,4'- biphenyltetracarboxylic dianhydride, 4,4'(to benzene) two ether dianhydrides, 3,3', 4,4'- bis-
Benzophenone tetracarboxylic acid dianhydride, bis- (3,4- dicarboxyphenyi) methane dianhydrides, 2,2'- bis- (3,4- bis- carboxy phenyl) hexafluoropropane tetracids
At least one of dianhydride.
5. the preparation method of polyimides ionomer according to claim 1, which is characterized in that the solvent is selected from first
Benzene, n,N-dimethylacetamide, at least one of N-Methyl pyrrolidone.
6. the preparation method of polyimides ionomer according to claim 4, which is characterized in that when the solvent is toluene
When, drying temperature is 50-70 DEG C；When solvent is n,N-dimethylacetamide, drying temperature is 70-90 DEG C；When solvent is N-
When methyl pyrrolidone, drying temperature is 70-90 DEG C.
7. the preparation method of polyimides ionomer according to claim 1, which is characterized in that the calcium hydroxide particle
Partial size be 1-50 μm.
8. the preparation method of polyimides ionomer according to claim 1, which is characterized in that the step of the substep heating
Suddenly are as follows:
1h at 100 DEG C, 1h at 150 DEG C, 1h at 200 DEG C, 1h at 250 DEG C, 1h at 300 DEG C；Or
1h at 100 DEG C, 1h at 200 DEG C, 2h at 300 DEG C.
9. a kind of polyimides ionomer, which is characterized in that the polyimides ionomer is by any one of claim 1-8 institute
The method stated prepares.
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| CN106902652B (en) * | 2017-03-21 | 2019-12-27 | 中国科学院兰州化学物理研究所 | Gas separation membrane with shape memory performance |
| EP3674349B1 (en) * | 2018-12-31 | 2024-04-10 | SHPP Global Technologies B.V. | Polyimide from metal free ionomers background |
| CN109880126B (en) * | 2019-02-22 | 2021-10-08 | 黑龙江省科学院石油化学研究院 | Polyimide precursor gel capable of preparing polyimide with high strength and heat resistance and light complex structure and application |
| CN110600745A (en) * | 2019-09-05 | 2019-12-20 | 东莞市烯热材料科技有限公司 | Preparation method of novel polyimide composite negative current collector for lithium ions |
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