CN105254888A - Polyimide ionomer and preparation method thereof - Google Patents
Polyimide ionomer and preparation method thereof Download PDFInfo
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- CN105254888A CN105254888A CN201510815178.6A CN201510815178A CN105254888A CN 105254888 A CN105254888 A CN 105254888A CN 201510815178 A CN201510815178 A CN 201510815178A CN 105254888 A CN105254888 A CN 105254888A
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Abstract
The invention discloses a preparation method of a polyimide ionomer, which comprises the following steps: at a temperature of 0-25 DEG C, under the protection condition of inert gas, continuing to stir for dissolving diamine in a solvent; weighing dianhydrides which are equal in molar ratio, adding the dianhydrides in batches, additionally adding a solvent, and continuing to stir, so that a high-viscosity polyamic acid solution is obtained; adding calcium hydroxide particles in the polyamic acid solution, and further stirring for reaction, so that a uniform and transparent polyamide salt solution is obtained; and flatly laying the polyamide salt solution on a substrate, drying for removing the solvent, and carrying out stepwise temperature-rising thermal imidization on the obtained object, so that a polyimide ionomer film is obtained. The invention also provides a polyimide ionomer prepared according to the method above. The polyimide ionomer has high-temperature shape memory properties.
Description
Technical field
The present invention relates to a kind of polyimide ionomer and preparation method thereof, particularly a kind of high-temperature shape-memory polyimide ionomer and preparation method thereof of calcium ion crosslinking.
Background technology
Shape-memory material refers to the change that shape can occur under extraneous conditioned stimulus, and keeps this temporary transient deformation under certain condition, and can be returned to a class material of original-shape when incentive condition applies again.Compare with shape memory ceramics with shape memory alloy, it is low that shape-memory polymer (SMP) has density, and deformation quantity is large, and cost is low, and processing preparation is simple to be waited many merits and receives much concern.Based on these advantages, SMP is at biomedical devices, and intelligent textile materials, 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.Reversiblely fixing temporary shapes by the phase-state change in phase in version process, can be crystallization-melting transition or vitreous state-unformed transformation.Stationary phase plays a part material with memory original-shape, can be physical crosslinking point or chemically crosslinked point.The SMP material studied at present mainly contains [ProgressinPolymerScience, 2012,37 (12): 1720-1763] such as urethane, polyolefine, epoxy resin, polyacrylic ester.Voit etc. report a kind of heat curing-type polymethacrylate copolymer, and its highest reversible recovery strain can reach 800% [AdvancedFunctionalMaterials, 2010,20 (1): 162-171].A kind of biocompatibility SMP material that then adopted the method for photo-crosslinking to prepare such as Shandas, have studied its application [Biomaterials, 2007,28 (14): 2255-2263] in angiocarpy bracket.Zhang etc. have then prepared a kind of poly(lactic acid)-carbonic ether shape memory multipolymer, have studied its application [ACSAppliedMaterials & Interfaces, 6 (4): 2611-2621] in bionic fiber support.
By suitable molecular designing, although above-mentioned polymer materials can embody higher shape-memory properties, also there are some shortcomings, such as lower physical strength, response temperature (lower than 150 DEG C) and restoring force etc.The application of these materials of these drawbacks limit in the environment that some are comparatively harsh, as hot environment, space environment etc.Therefore, preparing a kind of high temperature SMP with high strength is when previous important research topic.
Polyimide refers to the base polymer containing imide ring (-CO-NH-CO-) on main chain, wherein important with the polymkeric substance containing phthalimide structure.It is excellent etc. a little that polyimide has high temperature resistant, radiation hardness, mechanical property, as the special engineered material of one, has been widely used in the fields such as Aeronautics and Astronautics, microelectronics, nanometer, liquid crystal, separatory membrane, laser.But without the polyimide of particular design, can not shape memory characteristic be embodied.For this reason, ionization, according to the two phase structure mechanism of SMP, is introduced polyimide and is prepared a kind of novel ionomers by the present invention, can embody excellent physical strength and shape-memory properties.
Summary of the invention
The invention provides the ionomeric preparation method of a kind of polyimide, comprising:
At 0-25 DEG C, under protection of inert gas condition, diamines is dissolved in solvent by Keep agitation; The dianhydride taking equimolar amount adds in batches, and adds solvent, continues to stir, and obtains the polyamic acid solution that viscosity is higher;
Calcium hydroxide particle is added in polyamic acid solution, further stirring reaction, obtain the polyamic acid salts solution of homogeneous transparent;
Polyamic acid salts solution is laid on substrate, dry with desolvation, then obtain polyimide ionomer films by substep intensification hot imidization.
Further, the time controling that the dianhydride taking equimolar amount described in adds in batches added in 15-30min minute.
Further, described diamines is selected from 4,4'-diaminodiphenyl oxide, and 3,4'-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl-methane, 1, two (4-amino-benzene oxygen) benzene of 4-, two (4-amino-benzene oxygen) methane, 4,4'-diamino-3,3'-dimethyl diphenyl, 3,3'-dimethyl-4,4'-benzidine, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, at least one in two (4'-aminophenyl) hexanaphthene of 1,1-.
Further, described dianhydride is selected from 3,3', and 4,4'-oxydiphthalic, 3,3', 4,4'-BPDA, 4,4'(is to benzene) two ether dianhydrides, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyphenyi) methane dianhydride, at least one in two (3,4-bis-carboxyphenyl) the HFC-236fa tetracarboxylic dianhydride of 2,2'-.
Further, described solvent is selected from toluene, N,N-dimethylacetamide, at least one in N-Methyl pyrrolidone.
Further, when described solvent is toluene, drying temperature is 50-70 DEG C; When solvent is N,N-dimethylacetamide, drying temperature is 70-90 DEG C; When solvent is N-Methyl pyrrolidone, drying temperature is 70-90 DEG C.
Further, in described polyamic acid solution, solid content controls at 8-16wt%.
Further, the particle diameter of described calcium hydroxide particle is 1-50 μm.
Further, the step that described substep heats up is:
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.
The present invention also provides a kind of further and obtains a kind of polyimide ionomer by aforesaid method.
Polyimide ionomer provided by the invention and preparation method thereof, has the following advantages:
1. calcium ion crosslinking effect is introduced polyimide network by comparatively simple method by the present invention, prepare a kind of new type polyimide ionomer, the introducing of ionomer effect can improve the mechanical property of material, be used as stationary phase with ionomer, material has excellent shape-memory properties simultaneously.
2. the ionomeric second-order transition temperature of polyimide of the present invention can reach more than 270 DEG C, at high temperature can realize shape-memory properties, overcome the defect of SMP comparatively low-response temperature (mostly lower than 150 DEG C) conventional at present, ensure that it can be applied to the intelligent material of high-temperature field.
3. the storage modulus of polyimide ionomer of the present invention when room temperature (25 DEG C) vitreous state can reach more than 2.8GPa, can ensure size and the shape stability of component when using as structured material.
4. polyimide ionomer of the present invention can reach more than 35MPa when high temperature (300 DEG C) rubbery state, while guarantee has higher shape fixed rate, also have higher recovery of shape power and recovery of shape speed, its 180 DEG C of curved shapes only need 5-15s turnaround time.
5. preparation method of the present invention also has technique simply, is easy to the features such as suitability for industrialized production.
Accompanying drawing explanation
The ionomeric preparation method's schema of polyimide that Fig. 1 provides for the embodiment of the present invention.
The ionomeric structural representation of polyimide that Fig. 2 provides for the embodiment of the present invention.
The ionomeric stereoscan photograph of polyimide that Fig. 3 provides for the embodiment of the present invention.
The ionomeric out-of-phase modulus curve of polyimide (tan δ) that Fig. 4 provides for the embodiment of the present invention and storage modulus curve (E ').
The ionomeric shape memory cyclic curve of polyimide that Fig. 5 provides for the embodiment of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.Be understandable that, specific embodiment described herein is only for explaining the present invention, but not limitation of the invention.It also should be noted that, for convenience of description, illustrate only part related to the present invention in accompanying drawing but not entire infrastructure.
Please refer to Fig. 1, the embodiment of the present invention provides a kind of polyimide ionomeric preparation method, comprising:
S1, at 0-25 DEG C, under protection of inert gas condition, diamines is dissolved in solvent by Keep agitation; The dianhydride taking equimolar amount adds in batches, and adds solvent and continue to stir, and obtains the polyamic acid solution that viscosity is higher;
S2, adds calcium hydroxide particle in polyamic acid solution, further stirring reaction, obtains the polyamic acid salts solution of homogeneous transparent; And
S3, is laid on substrate by polyamic acid salts solution, dry with desolvation, then obtains polyimide ionomer films by substep intensification hot imidization.
In step sl, described rare gas element can be rare gas, nitrogen etc.The churning time that diamines is dissolved in solvent by described Keep agitation is 30-60min.The time controling that the described dianhydride taking equimolar amount adds in batches added in 15-30min minute.Described add solvent and continue stir churning time be 16-32h.Described diamines is selected from 4,4'-diaminodiphenyl oxide, 3,4'-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl-methane, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) methane, 4,4'-diamino-3,3'-dimethyl diphenyl, 3,3'-dimethyl-4,4'-benzidine, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, at least one in two (4'-aminophenyl) hexanaphthene of 1,1-.Described dianhydride is selected from 3,3', 4,4'-oxydiphthalic, 3,3', 4,4'-BPDA, 4,4'(is to benzene) two ether dianhydrides, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyphenyi) methane dianhydride, at least one in two (3,4-bis-carboxyphenyl) the HFC-236fa tetracarboxylic dianhydride of 2,2'-.Described solvent is selected from toluene, N,N-dimethylacetamide, at least one in N-Methyl pyrrolidone.In described polyamic acid solution, solid content controls at 8-16wt%, to obtain higher viscosity.
In step s 2, the particle diameter of described calcium hydroxide particle is 1-50 μm.Preferably, the particle diameter of described calcium hydroxide particle is 10-30 μm.Preferred, the particle diameter of described calcium hydroxide particle is 20-30 μm.Be appreciated that the calcium hydroxide particle adding different content, prepared ionomeric ionomer degree can be regulated.Described further stirring reaction, the churning time obtaining the polyamic acid salts solution of homogeneous transparent is 48-120h.
It is in step s3, described that by polyamic acid salts solution, the thickness be laid on substrate is 10 μm-500 μm.The temperature of described drying is 50-90 DEG C, and time of drying is 3-6h.Experiment proves, according to the difference of selected solvent, needs to select suitable drying temperature, is as the criterion to control evaporation rate and to avoid bubble to produce.When described solvent is toluene, drying temperature is preferably 50-70 DEG C; When solvent is N,N-dimethylacetamide, drying temperature is preferably 70-90 DEG C; When solvent is N-Methyl pyrrolidone, drying temperature is preferably 70-90 DEG C.Further, the step that described substep heats up is:
1) 1h, 1h at 150 DEG C, 1h at 200 DEG C, 1h at 250 DEG C, 1h at 300 DEG C at 100 DEG C; Or
2) 1h, 1h at 200 DEG C, 2h at 300 DEG C at 100 DEG C.
The present invention also provides a kind of further and obtains a kind of polyimide ionomer by aforesaid method.
Embodiment 1
Under room temperature condition, take 2.0g (0.01mol) 4,4'-diaminodiphenyl oxide (ODA) and be dissolved in the N-Methyl pyrrolidone of 25mL, Keep agitation 30min under N2 protection.Take 3.1g (0.01mol) 3,3', 4,4'-oxydiphthalic (ODPA), adds above solution in batches, and the N-Methyl pyrrolidone of 25mL is added in gradation simultaneously, add in 20min, reaction 24h obtains the polyamic acid solution of thickness further.Taking 0.037g (0.5mmol) calcium hydroxide adds in polyamic acid solution, continues reaction 72h, until solution is become from muddiness and clarifies completely, obtain polyamic acid salts solution in N2 protection is lower.Be laid on sheet glass by gained solution, prior to 80 DEG C of dry 4h, then carry out hot imidization, concrete temperature-rise period is 1h at 100 DEG C, 1h at 200 DEG C, 2h at 300 DEG C.Finally obtain the polyimide ionomer films that thickness is 50-200 μm.
Please refer to Fig. 2-3, the ionomeric sign of polyimide and shape-memory properties test: utilize scanning electron microscopic observation ionomer cross-section morphology, Latitudinal section many nano level projections and pit, indicates the enhancement to material of ionomer point; The infrared spectra of bond material, shows that calcium hydroxide forms ionomer network in polyamic acid complete reaction.Ionomeric second-order transition temperature is its recovery of shape temperature, closely related with its chain movement ability.The degree of crosslinking generally improving material can reduce the motor capacity of polymer chain, thus improves its second-order transition temperature.Utilize dynamic thermomechanical analysis apparatus (DMA) to measure the out-of-phase modulus curve (tan δ) of material and storage modulus curve (E '), drawn the second-order transition temperature of material by out-of-phase modulus peak.DMA experiment uses DMA242C to carry out with stretch mode, and experiment parameter is: constant frequency 1Hz, peak swing 60 μm, heating rate 5 DEG C of min
-1.As can be seen from accompanying drawing 4, the introducing of ionomer point, makes ionomeric second-order transition temperature bring up to 274.0 DEG C by 260.7 DEG C of PI.Simultaneously as can be seen from the storage modulus curve of accompanying drawing 4, the storage modulus that material is positioned at elastomeric state improves 34.9MPa by the 15.0MPa of PI, shows that the restoring force of material and reply speed are obtained for obvious lifting.
The same DMA that adopts of shape-memory properties test of material carries out, and cyclic tension program used is: be ε by initial strain
0sample is heated to 325 DEG C and applies a constant external force, reduces temperature to 20 DEG C and keeps 5min to obtain maximum strain ε
m; Remove external force and keep 5min to obtain temporary strian ε
u; Again be warming up to 325 DEG C, and keep 1h to obtain recovery strain ε
p.After this continue to repeat this circulation.Figure 5 provides an ionomeric shape memory cyclic curve.Shape fixed rate (R
f) and shape recovery rate (R
r) formula as follows:
R
f＝(ε
u-ε
0)/(ε
m-ε
0)
R
r＝(ε
u-ε
p)/(ε
u-ε
0)
Using ionomer point as stationary phase, material has good shape-memory properties, and its shape fixed rate and shape recovery rate can reach more than 99% and 90% respectively.
Embodiment 2
Substantially the same manner as Example 1, difference is, adds 0.074g (1mmol) calcium hydroxide, continues reaction 120h, until solution becomes clarification from muddiness.
The transition temperature of material, shape fixed rate and shape recovery rate is measured by the method for embodiment 1.The second-order transition temperature of material is 276.8 DEG C, and its shape fixed rate and shape recovery rate can reach more than 99% and 80% respectively.
Embodiment 3
Substantially the same manner as Example 1, difference is, selects 3,3', and 4,4'-BPDA prepares polyamic acid as dianhydride monomer, and the calcium hydroxide adding 0.0074g (0.1mmol) continues reaction 48h.
The transition temperature of material, shape fixed rate and shape recovery rate is measured by the method for embodiment 1.The second-order transition temperature of material is 275.5 DEG C, and its shape fixed rate and shape recovery rate can reach 97% and 93% respectively.
Embodiment 4
Substantially the same manner as Example 1, difference is, selects 3,3', and 4,4'-BPDA prepares polyamic acid as dianhydride monomer, adds 0.037g (0.5mmol) calcium hydroxide reaction 72h, obtains polyamic acid salts solution.
Shape fixed rate and the shape recovery rate of material is measured by the method for embodiment 1.The shape fixed rate of material and response rate can reach 98% and 90% respectively.
Embodiment 5
Substantially the same manner as Example 1, difference is, selects 3,4'-diaminodiphenyl oxide to prepare polyamic acid as diamines.
Shape fixed rate and the shape recovery rate of material is measured by the method for embodiment 1.The shape fixed rate of material and response rate can reach 98% and 90% respectively.
Embodiment 6
Substantially the same manner as Example 1, difference is, selects two (3,4-bis-carboxyphenyl) the HFC-236fa tetracarboxylic dianhydride of 2,2'-to be that dianhydride prepares polyamic acid.
Shape fixed rate and the shape recovery rate of material is measured by the method for embodiment 1.The shape fixed rate of material and response rate can reach 97% and 90% respectively.
Note, above are only preferred embodiment of the present invention and institute's application technology principle.Skilled person in the art will appreciate that and the invention is not restricted to specific embodiment described here, various obvious change can be carried out for a person skilled in the art, readjust and substitute and can not protection scope of the present invention be departed from.Therefore, although be described in further detail invention has been by above embodiment, the present invention is not limited only to above embodiment, when not departing from the present invention's design, can also comprise other Equivalent embodiments more, and scope of the present invention is determined by appended right.
Claims (10)
1. the ionomeric preparation method of polyimide, comprising:
At 0-25 DEG C, under protection of inert gas condition, diamines is dissolved in solvent by Keep agitation; The dianhydride taking equimolar amount adds in batches, and adds solvent, continues to stir, and obtains the polyamic acid solution that viscosity is higher;
Calcium hydroxide particle is added in polyamic acid solution, further stirring reaction, obtain the polyamic acid salts solution of homogeneous transparent;
Polyamic acid salts solution is laid on substrate, dry with desolvation, then obtain polyimide ionomer films by substep intensification hot imidization.
2. the ionomeric preparation method of polyimide according to claim 1, is characterized in that, described in take equimolar amount the time controling that in batches adds of dianhydride added in 15-30min minute.
3. the ionomeric preparation method of polyimide according to claim 1, is characterized in that, described diamines is selected from 4,4'-diaminodiphenyl oxide, 3,4'-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl-methane, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) methane, 4,4'-diamino-3,3'-dimethyl diphenyl, 3,3'-dimethyl-4,4'-benzidine, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, at least one in two (4'-aminophenyl) hexanaphthene of 1,1-.
4. the ionomeric preparation method of polyimide according to claim 1, is characterized in that, described dianhydride is selected from 3,3', 4,4'-oxydiphthalic, 3,3', 4,4'-BPDA, 4,4'(is to benzene) two ether dianhydrides, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyphenyi) methane dianhydride, at least one in two (3,4-bis-carboxyphenyl) the HFC-236fa tetracarboxylic dianhydride of 2,2'-.
5. the ionomeric preparation method of polyimide according to claim 1, is characterized in that, described solvent is selected from toluene, N,N-dimethylacetamide, at least one in N-Methyl pyrrolidone.
6. the ionomeric preparation method of polyimide according to claim 4, is characterized in that, when described solvent is toluene, drying temperature is 50-70 DEG C; When solvent is N,N-dimethylacetamide, drying temperature is 70-90 DEG C; When solvent is N-Methyl pyrrolidone, drying temperature is 70-90 DEG C.
7. the ionomeric preparation method of polyimide according to claim 1, is characterized in that, in described polyamic acid solution, solid content controls at 8-16wt%.
8. the ionomeric preparation method of polyimide according to claim 1, is characterized in that, the particle diameter of described calcium hydroxide particle is 1-50 μm.
9. the ionomeric preparation method of polyimide according to claim 1, is characterized in that, the step that described substep heats up is:
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.
10. a polyimide ionomer, is characterized in that, the method for described polyimide ionomer according to any one of claim 1-9 prepares.
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| 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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