WO2015176545A1 - High temperature-resistant thermoplastic shape-memory polyimide and preparation method therefor - Google Patents

High temperature-resistant thermoplastic shape-memory polyimide and preparation method therefor Download PDF

Info

Publication number
WO2015176545A1
WO2015176545A1 PCT/CN2015/070308 CN2015070308W WO2015176545A1 WO 2015176545 A1 WO2015176545 A1 WO 2015176545A1 CN 2015070308 W CN2015070308 W CN 2015070308W WO 2015176545 A1 WO2015176545 A1 WO 2015176545A1
Authority
WO
WIPO (PCT)
Prior art keywords
temperature
shape memory
high temperature
resistant thermoplastic
raised
Prior art date
Application number
PCT/CN2015/070308
Other languages
French (fr)
Chinese (zh)
Inventor
冷劲松
肖鑫礼
刘彦菊
孔德艳
Original Assignee
哈尔滨工业大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 哈尔滨工业大学 filed Critical 哈尔滨工业大学
Publication of WO2015176545A1 publication Critical patent/WO2015176545A1/en

Links

Images

Classifications

    • 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

Definitions

  • the invention relates to a shape memory polyimide and a preparation method thereof.
  • a shape memory polymer is a polymer material that has an initial shape and is deformed and fixed under certain conditions, and is capable of sensing and responding to external changes of the stimulus to restore its original state.
  • various SMP materials such as shape memory polyurethane, shape memory polystyrene and shape memory epoxy resin have been developed in the world [Nature, 2010, 464, 267-270.], which are used in many fields such as smart textile, biomedical, aerospace and many other fields. More and more important.
  • Thermoplastic SMP has the advantages of easy processing and convenient use, and has excellent application and research prospects.
  • Shape memory fibers are prepared by using shape memory polyurethane such as Hu, and the clothes woven with these fibers have a unique shape memory effect and waterproof moisture permeability [Polymer, 2009, 50, 4424-4428.].
  • T g glass transition temperature
  • Polyimide (PI) is an aromatic heterocyclic polymer containing an imide characteristic group in the main chain structural unit, and has the advantages of high temperature resistance, radiation resistance, excellent mechanical properties, and diverse processing paths, and has been widely used. Automotive, microelectronics, aerospace and other fields [polyimide: relationship between chemistry, structure and properties and materials, Science Press, 2012.09.]. Therefore, shape memory thermoplastic polyimide has broad application prospects in many fields.
  • Thermoplastic polyimide generally refers to a soluble polyimide having a linear macromolecular structure with meltable and dissolvable processability.
  • General Electric Company of the United States introduced the thermoplastic polyetherimide Ultem, which has excellent soluble melt processing properties and still has strong market competitiveness.
  • thermoplastic polyetherimide Aurum with excellent heat resistance and melt processability.
  • the product was prepared by extrusion method and sold under the trade name Regulus.
  • the Changchun Yinghua Institute of the Chinese Academy of Sciences began researching polyimides in the 1960s and developed the YHPI series of thermoplastic polyimides. These polyimides have high toughness and horniness and can be molded and injection molded. They have been widely used in electrical insulation and wear resistant materials.
  • the Shanghai Synthetic Resin Research Institute has developed the Ratem series of polyimide engineering plastics since the 1970s, which can be used as bars, plates, tubes and processed or sintered parts.
  • Vaia et al. reported a thermosetting polyimide SMP with a T g around 220 ° C [Polymer 2013, 54, 391-402.]. However, there are no reports of SMP with T g >300 °C at home and abroad.
  • the object of the present invention is to solve the problem that the existing shape memory polymer has a low glass transition temperature T g , poor thermal properties and thermodynamic properties at high temperatures, and cannot be applied in a high temperature field, and provides a high temperature resistant thermoplastic shape memory polyacyl group. Imine and its preparation method.
  • thermoplastic shape memory polyimide prepared by using 4,4'-(hexafluoroisopropene) diphthalic anhydride and 4,4'-diaminodiphenyl ether as a reactive monomer; The amount ratio of the 4'-(hexafluoroisopropene) diphthalic anhydride monomer to the 4,4'-diaminodiphenyl ether monomer was 1:1.
  • thermoplastic shape memory polyimide The structural formula of a high temperature resistant thermoplastic shape memory polyimide is:
  • n is from 128 to 172.
  • a method for preparing a high temperature resistant thermoplastic shape memory polyimide is accomplished by the following steps:
  • the volume ratio of the amount of the 4,4'-diaminodiphenyl ether monomer to the N,N'-dimethylacetamide in the first step is (0.1 mmol to 0.2 mmol): 1 mL;
  • sol-gel polyamic acid 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 3 to 6 times at room temperature and stirring speed was 300 r/min. Stirring for 25 to 30 hours under conditions of ⁇ 400/min to obtain a sol-gel polyamic acid;
  • the ratio of the amount of the 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer to the 4,4'-diaminodiphenyl ether monomer in the diamine solution is 1:1;
  • the sol-gel-like polystyrene acid is poured onto the substrate, and the temperature is raised from room temperature to 60 ° C to 90 ° C at a heating rate of 1 ° C / min to 2 ° C / min, and The temperature is maintained at 60 ° C ⁇ 90 ° C for 1 h ⁇ 2 h; then at 1 ° C / min ⁇ 2 ° C / min heating rate to 120 ° C ⁇ 140 ° C, and at a temperature of 120 ° C ⁇ 140 ° C for 1 h ⁇ 2h Then, the temperature is raised to 170 ° C ⁇ 190 ° C at a heating rate of 1 ° C / min ⁇ 2 ° C / min, and the temperature is maintained at 170 ° C ⁇ 190 ° C for 1 h ⁇ 2 h; and then 1 ° C / min ⁇ 2 ° C / min The heating rate is up to 220 ° C ⁇ 250 ° C,
  • the substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally at a temperature of 120 ° C to 180 ° C. The lower temperature is heated for 360 min to 600 min to obtain a high temperature resistant thermoplastic shape memory polyimide.
  • the chemical reaction formula in the second step of the present invention is:
  • the chemical reaction formula in the fourth step of the present invention is:
  • the high temperature thermoplastic shape memory polyimide prepared by the invention has a glass transition temperature T g of 313 ° C to 319 ° C, which makes it applicable to the field of high temperature shape memory polymers;
  • the material prepared by the invention can be dissolved in an organic solvent such as chloroform, toluene, xylene or N,N'-dimethylacetamide at room temperature at 25 ° C, and has excellent processability for low-temperature solvent processing;
  • the decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared by the invention is 5% when the mass loss is 5%, which indicates that the material has thermal stability at high temperature and can be used for a long time in a high temperature environment;
  • the high temperature resistant thermoplastic shape memory polyimide prepared by the invention has excellent thermodynamic effect, the storage modulus is greater than 2 GPa at a normal temperature of 30 ° C glass state, and the storage modulus at a high temperature (T g + 20 ° C) rubber state. More than 6 MPa; the stability of the size and shape of the structural member at high temperature is ensured;
  • the high temperature resistant thermoplastic shape memory polyimide prepared by the invention has excellent high and low temperature resistance, and its shape memory performance is not lowered after being heated for 100 hours in an alternating atmosphere of -120 ° C to 120 ° C.
  • the present invention provides a high temperature resistant thermoplastic shape memory polyimide.
  • Example 1 is an infrared spectrum diagram of a high temperature resistant thermoplastic shape memory polyimide prepared in Example 1;
  • Example 2 is a loss factor diagram of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1;
  • Example 3 is a storage modulus diagram of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1;
  • Example 4 is a thermogravimetric analysis diagram of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1;
  • Example 5 is a temporary shape obtained by bending a high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 at 310 ° C and fixing at room temperature;
  • Example 6 is a shape recovery state of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 2 s on a hot stage at 310 ° C;
  • Example 7 is a shape recovery state of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 10 s on a hot stage at 310 ° C;
  • Example 8 is a shape recovery state of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 13 s on a hot stage at 310 ° C;
  • Example 9 is a shape recovery state of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 16 s on a hot stage at 310 ° C;
  • Figure 10 is a view showing the shape of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 restored to its original shape after 23 seconds on a hot stage at 310 °C.
  • the present embodiment is a high temperature resistant thermoplastic shape memory polyimide comprising 4,4'-(hexafluoroisopropene) dinonanhydride and 4,4'-diaminodiphenyl ether as a reactive monomer Prepared; the amount ratio of the 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer to the 4,4'-diaminodiphenyl ether monomer is 1:1.
  • thermoplastic shape memory polyimide This embodiment differs from the specific embodiment in that the structural formula of a high temperature resistant thermoplastic shape memory polyimide is:
  • n is from 128 to 172.
  • the other steps are the same as in the first embodiment.
  • This embodiment differs from the second embodiment in that a high temperature resistant thermoplastic shape memory polyimide has a weight average molecular weight of 77.8 kg/mol to 104.6 kg/mol.
  • the other steps are the same as in the second embodiment.
  • This embodiment is a method for preparing a high temperature resistant thermoplastic shape memory polyimide, which is completed as follows:
  • the volume ratio of the amount of the 4,4'-diaminodiphenyl ether monomer to the N,N'-dimethylacetamide in the first step is (0.1 mmol to 0.2 mmol): 1 mL;
  • sol-gel polyamic acid 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 3 to 6 times at room temperature and stirring speed was 300 r/min. Stirring for 25 to 30 hours under conditions of ⁇ 400/min to obtain a sol-gel polyamic acid;
  • the ratio of the amount of the 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer to the 4,4'-diaminodiphenyl ether monomer in the diamine solution is 1:1;
  • the sol-gel-like polystyrene acid is poured onto the substrate, and the temperature is raised from room temperature to 60 ° C to 90 ° C at a heating rate of 1 ° C / min to 2 ° C / min, and The temperature is maintained at 60 ° C ⁇ 90 ° C for 1 h ⁇ 2 h; then at 1 ° C / min ⁇ 2 ° C / min heating rate to 120 ° C ⁇ 140 ° C, and at a temperature of 120 ° C ⁇ 140 ° C for 1 h ⁇ 2h Then, the temperature is raised to 170 ° C ⁇ 190 ° C at a heating rate of 1 ° C / min ⁇ 2 ° C / min, and the temperature is maintained at 170 ° C ⁇ 190 ° C for 1 h ⁇ 2 h; and then 1 ° C / min ⁇ 2 ° C / min The heating rate is up to 220 ° C ⁇ 250 ° C,
  • the substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally at a temperature of 120 ° C to 180 ° C. The lower temperature is heated for 360 min to 600 min to obtain a high temperature resistant thermoplastic shape memory polyimide.
  • the high temperature thermoplastic shape memory polyimide prepared by the embodiment has a glass transition temperature T g of 313 ° C to 319 ° C, which can be applied to the field of high temperature shape memory polymers;
  • the material prepared in the present embodiment can be dissolved in an organic solvent such as chloroform, toluene, xylene or N,N'-dimethylacetamide at room temperature at 25 ° C, and has excellent processability for low-temperature solvent processing. ;
  • the decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared by the embodiment is 5% when the mass loss is 5%, which indicates that the material has thermal stability at high temperature and can be used for a long time in a high temperature environment;
  • the high temperature resistant thermoplastic shape memory polyimide prepared by the embodiment has excellent thermodynamic effect, the storage modulus is greater than 2 GPa at a normal temperature of 30 ° C glass state; the storage modulus at a high temperature of 337 ° C rubber state is greater than 6 MPa; The stability of the size and shape of the structural member at high temperatures;
  • the high temperature resistant thermoplastic shape memory polyimide prepared by the present embodiment has excellent high and low temperature resistance, and its shape memory performance is not lowered after being heated for 100 hours in an alternating atmosphere of -120 ° C to 120 ° C.
  • This embodiment provides a high temperature resistant thermoplastic shape memory polyimide.
  • Embodiment 7 This embodiment differs from one of the fifth or sixth embodiment in that: in step 3, the sol-gel polyamic acid is dried in a vacuum drying oven at 55 ° C to 75 ° C for 1.5 h to 2 h. A sol-gel-like polyamic acid containing no bubbles was obtained. The other steps are the same as the fifth or sixth embodiment.
  • BEST MODE 8 This embodiment differs from one of the fifth to seventh embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the sol-gel-like bubble-free is used.
  • the polyamic acid is poured onto the substrate, and the temperature is raised from room temperature to 70 ° C to 80 ° C at a heating rate of 1 ° C / min to 2 ° C / min, and the temperature is maintained at 70 ° C to 80 ° C for 1 h to 2 h;
  • the heating rate of °C/min ⁇ 2°C/min is raised to 130°C ⁇ 140°C, and the temperature is maintained at 130°C ⁇ 140°C for 1h ⁇ 2h; then the temperature is raised at the heating rate of 1°C/min ⁇ 2°C/min.
  • This embodiment differs from one of the fifth to eighth embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate at a heating rate of 1 ° C/min.
  • the temperature was raised to 60 ° C at room temperature, and the temperature was maintained at 60 ° C for 2 h; then the temperature was raised to 120 ° C at a heating rate of 1 ° C / min, and kept at a temperature of 120 ° C for 1 h; then at a heating rate of 1 ° C / min
  • the temperature is raised to 170 ° C, and the temperature is maintained at 170 ° C for 1 h; then at a temperature increase rate of 1 ° C / min to 220 ° C, and the temperature is maintained at 220 ° C for 1 h; and then heated at a temperature increase rate of 1 ° C / min to 270 °C, and kept at a temperature of 270 ° C for 1 h; then at a temperature increase rate of 1 ° C / min to 330 ° C, and at a temperature of 330 ° C for 1 h; finally at a temperature of 1 ° C / min from the temperature of 330 ° C
  • the substrate
  • step 4 a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate at a heating rate of 1 ° C/min. The temperature was raised to 60 ° C at room temperature, and the temperature was kept at 60 ° C for 2 h; then the temperature was raised to 120 ° C at a heating rate of 1 ° C / min, and the temperature was 120 ° C.
  • step 4 a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate at a heating rate of 1 ° C/min.
  • the temperature was raised from room temperature to 70 ° C, and the temperature was kept at 70 ° C for 2 h; then the temperature was raised to 140 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 140 ° C for 2 h; then at a heating rate of 1 ° C / min
  • the temperature is raised to 180 ° C, and the temperature is maintained at 180 ° C for 1 h; then at a temperature increase rate of 2 ° C / min to 250 ° C, and the temperature is maintained at 250 ° C for 1 h; and then heated at a rate of 2 ° C / min to 290 °C, and kept at a temperature of 290 ° C for 1 h; then at a temperature increase rate of 2 ° C / min to 320 ° C, and at a temperature of 320 ° C for 1 h; finally at a temperature of 2 ° C / min from 320 ° C
  • the substrate was cooled to room temperature to obtain a
  • step 4 a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 1 ° C/min.
  • the temperature is raised from room temperature to 80 ° C, and the temperature is kept at 80 ° C for 2 h; then the temperature is raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 130 ° C for 2 h; then the temperature is raised at 1 ° C / min
  • the temperature is raised to 180 ° C, and the temperature is maintained at 180 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 230 ° C, and the temperature is maintained at 230 ° C for 1 h; and then heated at a temperature increase rate of 2 ° C / min to 280 ° C, and incubated at 280 ° C for 1 h; then at 2 ° C / min heating rate to 330 ° C, and at a temperature of 330 ° C for 1 h; finally at 2 ° C / min cooling rate from a temperature of 330
  • the temperature was lowered to room temperature at ° C to obtain a
  • step 4 a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 1 ° C/min.
  • the temperature is raised from room temperature to 80 ° C, and the temperature is kept at 80 ° C for 2 h; then the temperature is raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 130 ° C for 2 h; then the temperature is raised at 1 ° C / min
  • the temperature is raised to 180 ° C, and the temperature is maintained at 180 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 230 ° C, and the temperature is maintained at 230 ° C for 2 h; and then heated at a temperature increase rate of 2 ° C / min to 280 ° C, and incubated at 280 ° C for 1 h; then at 2 ° C / min heating rate to 330 ° C, and at a temperature of 330 ° C for 1 h; finally at 2 ° C / min cooling rate from a temperature of 330
  • the temperature was lowered to room temperature at ° C to obtain a
  • This embodiment differs from one of the fifth to thirteenth embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 1 ° C/min.
  • the temperature is raised from room temperature to 80 ° C, and the temperature is kept at 80 ° C for 2 h; then the temperature is raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 130 ° C for 2 h; then the temperature is raised at 1 ° C / min
  • the temperature is raised to 180 ° C, and the temperature is maintained at 180 ° C for 2 h; then at a temperature increase rate of 1 ° C / min to 240 ° C, and the temperature is maintained at 240 ° C for 1 h; and then heated at a temperature increase rate of 1 ° C / min to 280 ° C, and incubated at a temperature of 280 ° C for 1 h; then at a temperature increase rate of 1 ° C / min to 330 ° C, and at a temperature of 330 ° C for 1 h; finally at a rate of 1 ° C / min from the temperature of 330
  • the temperature was lowered to room
  • This embodiment differs from one of the fifth to fourteenth embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 1 ° C/min.
  • the rate starts to increase from room temperature to 70 ° C, and the temperature is maintained at 70 ° C for 2h; then at a temperature increase rate of 1 ° C / min to 130 ° C, and the temperature is maintained at 130 ° C for 2h; and then heated at a temperature of 1 ° C / min to 180 ° C, And the temperature is maintained at 180 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 240 ° C, and the temperature is maintained at 240 ° C for 1 h; then at a temperature increase rate of 2 ° C / min to 280 ° C, and at the temperature The temperature was kept at 280 ° C for 1 h; the temperature was raised to 330 ° C at a heating rate of 2 ° C / min, and the temperature was maintained at 330 ° C for 1 h; finally, the temperature was lowered from 330 ° C to room temperature at a cooling rate of 2 ° C / min.
  • step 4 a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 1 ° C/min.
  • the temperature is raised from room temperature to 70 ° C, and the temperature is kept at 70 ° C for 2 h; then the temperature is raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 130 ° C for 2 h; then the temperature is raised at 1 ° C / min
  • the temperature is raised to 180 ° C, and the temperature is maintained at 180 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 240 ° C, and the temperature is maintained at 240 ° C for 1 h; and then heated at a temperature increase rate of 2 ° C / min to 280 ° C, and incubated at 280 ° C for 1 h; then at 2 ° C / min heating rate to 330 ° C, and at a temperature of 330 ° C for 1 h; finally at 2 ° C / min cooling rate from a temperature of 330
  • the temperature was lowered to room temperature at ° C to obtain a
  • step 4 a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate at a heating rate of 1 ° C/min.
  • the temperature was raised from room temperature to 80 ° C, and the temperature was kept at 80 ° C for 2 h; then the temperature was raised to 140 ° C at a heating rate of 1 ° C / min, and kept at a temperature of 140 ° C for 2 h; and then at a heating rate of 1 ° C / min
  • the temperature is raised to 190 ° C, and the temperature is maintained at 190 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 250 ° C, and the temperature is maintained at 250 ° C for 1 h; and then heated at a temperature increase rate of 2 ° C / min to 290 °C, and kept at a temperature of 290 ° C for 2h; then heated to 340 ° C at a temperature increase rate of 2 ° C / min, and incubated at a temperature of 340 ° C for 2 h; finally at a temperature drop of 2 ° C / min from a temperature of 340 ° C
  • step 4 a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 2 ° C/min.
  • the temperature is raised from room temperature to 90 ° C, and the temperature is maintained at 90 ° C for 2 h; then the temperature is raised to 140 ° C at a temperature increase rate of 2 ° C / min, and the temperature is maintained at 140 ° C for 2 h; then the temperature is raised at 2 ° C / min
  • the temperature is raised to 190 ° C, and the temperature is maintained at 190 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 250 ° C, and the temperature is maintained at 250 ° C for 2 h; and then heated at a temperature increase rate of 2 ° C / min to 290 ° C, and incubated at a temperature of 290 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 340 ° C, and at a temperature of 340 ° C for 2 h; finally at a rate of 2 ° C / min from the temperature of 340
  • the temperature was lowered to
  • This embodiment differs from one of the fifth to nineteenth embodiments in the specific embodiment in that the amount of the substance of the 4,4'-diaminodiphenyl ether monomer described in the first step is N, N'- The volume ratio of the dimethylacetamide solvent was 0.1 mmol: 1 mL.
  • the other steps are the same as the specific embodiments 5 to 19.
  • This embodiment differs from the specific embodiment 6 to 21 in that the amount of the 4,4'-diaminodiphenyl ether monomer in step 1 is N, N' The volume ratio of the dimethylacetamide solvent was 0.14 mmol: 1 mL.
  • the other steps are the same as the specific embodiments 6 to 20.
  • This embodiment differs from one of the fifth to twenty-first embodiments in the following manner: the amount of the substance of the 4,4'-diaminodiphenyl ether monomer described in the first step is N, N. The volume ratio of '-dimethylacetamide solvent was 0.15 mmol: 1 mL. The other steps are the same as the specific embodiments 5 to 21.
  • This embodiment differs from one of the fifth to twenty-fourth embodiments in the specific embodiment in that the amount of the substance of the 4,4'-diaminodiphenyl ether monomer described in the first step is N, N.
  • the volume ratio of the '-dimethylacetamide solvent was 0.18 mmol: 1 mL.
  • the other steps are the same as the specific embodiments 5 to 24.
  • This embodiment differs from one of the fifth to twenty-seventh embodiments in that: in step 5, the substrate of the polyamide film is placed in distilled water to make the polyamide film from the substrate of the polyamide film. After falling off, the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 130 ° C to 170 ° C for 450 min to 550 min to obtain a high temperature resistant thermoplastic shape memory polyimide. The other steps are the same as the specific embodiments 5 to 27.
  • Example 1 A method for preparing a high temperature resistant thermoplastic shape memory polyimide was carried out by the following steps:
  • sol-gel polyamic acid 1.9 mmol of 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 5 portions at room temperature and the stirring speed was 400 r / Stirring under the condition of min for 28 h to obtain a sol-gel polyamic acid;
  • thermal imidization the sol-gel-like polystyrene acid is poured onto the substrate, the temperature is raised from room temperature to 80 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 80 ° C for 2 h; Then, the temperature was raised to 140 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 140 ° C for 2 h; then the temperature was raised to 190 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 190 ° C for 2 h; The heating rate of °C/min is up to 250 °C, and the temperature is maintained at 250 ° C for 1 h; then the temperature is raised to 290 ° C at a heating rate of 2 ° C / min, and the temperature is maintained at 290 ° C for 2 h; then 2 ° C / min The heating rate is raised to 340 ° C, and the temperature is kept at 340 ° C for 2
  • the substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 120 ° C for 500 min. A high temperature resistant thermoplastic shape memory polyimide is obtained.
  • the high temperature thermoplastic shape memory polyimide prepared in Example 1 was measured by gel permeation chromatography to have a weight average molecular weight of 101 kg/mol.
  • thermoplastic shape memory polyimide prepared in Example 1 was measured by gel permeation chromatography:
  • FIG. 1 is an infrared spectrum diagram of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1.
  • symmetric stretching vibration peak (v s C O)
  • an absorption peak at 1382cm -1 (V CN) CN bond stretching vibration at 1110cm -1 imide ring was bending vibration absorption peaks (v CO).
  • FIG. 2 is a loss factor diagram of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1. . It can be seen from FIG. 2 that the glass transition temperature T g of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 is 317 ° C, and thus it can be seen that the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 can be applied. To the high temperature field.
  • FIG. 3 is a storage modulus diagram of the high temperature resistant thermoplastic shape memory polyimide; It can be seen that the modulus change curve shows two platforms in the high and low temperature sections, and the storage modulus at room temperature, that is, the glass state at 30 ° C is 2243 MPa; the storage modulus at the high temperature of 337 ° C, that is, the rubber state at T g + 20 ° C About 9.7 MPa; the storage modulus drops sharply between the two platforms, corresponding to the glass transition process of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1, the sharp change of the modulus is the polymer The necessary conditions for shape memory properties.
  • the corresponding storage modulus at 287 ° C, ie T g -30 ° C, is 1142 MPa, which ensures that the high temperature resistant thermoplastic shape memory polyimide of Example 1 is used as a structural material, which is higher than the current SMP materials.
  • the change in modulus within the use temperature range is relatively small, and the dimensional and shape stability of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 as a structural member is ensured.
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 was tested using a thermogravimetric analyzer as shown in FIG. 4; and FIG. 4 is a thermogravimetric analysis diagram of the high temperature resistant thermoplastic shape memory polyimide. 4, the decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 was 525 ° C when the mass loss was 5%, and the residual temperature at 800 ° C was 56.2%, indicating the high temperature resistance prepared in Example 1. Thermoplastic shape memory polyimides have excellent heat resistance.
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 was tested using a high temperature hot stage, as shown in FIGS. 5 to 10;
  • FIG. 5 is a high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 at 310.
  • the temporary shape prepared by bending at ° C and fixed at room temperature;
  • FIG. 6 is the shape recovery of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 2 s on a hot stage at 310 ° C;
  • FIG. 7 is the resistance of Example 1 The shape recovery of the high temperature thermoplastic shape memory polyimide after 10s on the hot stage at 310 ° C;
  • FIG. 5 is a high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 at 310.
  • the temporary shape prepared by bending at ° C and fixed at room temperature
  • FIG. 6 is the shape recovery of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 2 s on a hot stage at 310 ° C
  • FIG. 7 is the resistance of Example
  • Example 2 A method for preparing a high temperature resistant thermoplastic shape memory polyimide was carried out by the following steps:
  • sol-gel polyamic acid 1 mmol of 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 4 portions at room temperature and the stirring speed was 300 r/min. Stirring under the conditions of 26 h to obtain a sol-gel polyamic acid;
  • thermal imidization the sol-gel-like polystyrene acid is poured onto the substrate, the temperature is raised from room temperature to 70 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 70 ° C for 2 h; Then, the temperature was raised to 140 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 140 ° C for 2 h; then the temperature was raised to 180 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 180 ° C for 1 h; The heating rate of °C/min is up to 250 °C, and the temperature is maintained at 250 ° C for 1 h; then the temperature is raised to 290 ° C at a heating rate of 2 ° C / min, and the temperature is maintained at 290 ° C for 1 h; then 2 ° C / min The heating rate was raised to 320 ° C, and the temperature was kept at 320 ° C for 1 h
  • the substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 180 ° C for 400 min. A high temperature resistant thermoplastic shape memory polyimide is obtained.
  • the weight average molecular weight of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 2 was measured by gel permeation chromatography to be 77.8 kg/mol.
  • thermoplastic shape memory polyimide prepared in Example 2 was measured using a gel permeation chromatograph:
  • the glass transition temperature T g of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 2 was 313 °C.
  • the storage modulus at a normal temperature of 30 ° C in a glass state is 2012 MPa; the storage modulus at a high temperature of 333 ° C, that is, T g + 20 ° C in a rubber state is about 6.2 MPa.
  • the decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 2 at a mass loss of 5% was 522 ° C, and the residue at 800 ° C was 53.5%.
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 2 was folded 180° on a hot plate at 310 ° C to return to the original shape for 33 s.
  • Example 3 A method for preparing a high temperature resistant thermoplastic shape memory polyimide was carried out by the following steps:
  • sol-gel polyamic acid 1.5 mmol of 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 5 portions at room temperature and the stirring speed was 350 r / Stirring under the condition of min for 26 h to obtain a sol-gel polyamic acid;
  • thermal imidization the sol-gel-like polystyrene acid is poured onto the substrate, the temperature is raised from room temperature to 80 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 80 ° C for 2 h; Then, the temperature was raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 130 ° C for 2 h; then the temperature was raised to 180 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 180 ° C for 2 h; The heating rate of °C/min is up to 230 °C, and the temperature is kept at 230 °C for 2 h; then the temperature is raised to 280 °C at a heating rate of 2 °C/min, and the temperature is maintained at 280 °C for 1 h; then at 2 °C/min.
  • the heating rate was raised to 330 ° C, and the temperature was maintained at 330 ° C for 1 h; finally, the temperature was lowered from 330 ° C to room temperature at a cooling rate of 2 ° C / min to obtain a substrate of a polyamide film.
  • the substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 180 ° C for 360 min. A high temperature resistant thermoplastic shape memory polyimide is obtained.
  • the weight average molecular weight of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 3 was measured by gel permeation chromatography to be 88.8 kg/mol.
  • thermoplastic shape memory polyimide prepared in Example 3 was measured using a gel permeation chromatograph:
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 3 had a glass transition temperature Tg of 314 °C.
  • the storage modulus at room temperature, that is, the glass state at 30 ° C is 2126 MPa; the storage modulus at the high temperature of 334 ° C, that is, T g + 20 ° C in the rubber state is about 7.1 MPa.
  • the decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 3 at a mass loss of 5% was 524 ° C, and the residue at 800 ° C was 54.5%.
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 3 was folded 180° on a hot plate at 310 ° C to return to the original shape for 31 s.
  • Example 4 A method for preparing a high temperature resistant thermoplastic shape memory polyimide was carried out by the following steps:
  • sol-gel polyamic acid 1.7 mmol of 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 5 portions at room temperature and the stirring speed was 300 r / Stirring under the condition of min for 26 h to obtain a sol-gel polyamic acid;
  • thermal imidization the sol-gel-like polystyrene acid is poured onto the substrate, the temperature is raised from room temperature to 70 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 70 ° C for 2 h; Then, the temperature was raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 130 ° C for 2 h; then the temperature was raised to 180 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 180 ° C for 2 h; The heating rate of °C/min is up to 240 °C, and the temperature is kept at 240 °C for 1 h; then the temperature is raised to 280 °C at a heating rate of 2 °C/min, and the temperature is maintained at 280 °C for 1 h; then at 2 °C/min.
  • the heating rate was raised to 330 ° C, and the temperature was maintained at 330 ° C for 1 h; finally, the temperature was lowered from 330 ° C to room temperature at a cooling rate of 2 ° C / min to obtain a substrate of a polyamide film.
  • the substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 180 ° C for 400 min. A high temperature resistant thermoplastic shape memory polyimide is obtained.
  • the weight average molecular weight of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 4 was measured by gel permeation chromatography to be 94.2 kg/mol.
  • thermoplastic shape memory polyimide prepared in Example 4 was measured using a gel permeation chromatograph:
  • High Temperature Thermoplastic shape memory Preparation Example 4 polyimide has a glass transition temperature T g of 315 °C.
  • the storage modulus at room temperature, that is, the glass state at 30 ° C is 2176 MPa; the storage modulus at the high temperature of 335 ° C, that is, T g + 20 ° C in the rubber state is about 7.8 MPa.
  • the decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 4 at a mass loss of 5% was 523 ° C, and the residue at 800 ° C was 56.5%.
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 4 was folded 180° on a hot plate at 310 ° C to return to the original shape for 38 s.
  • Example 5 A method for preparing a high temperature resistant thermoplastic shape memory polyimide was carried out by the following steps:
  • sol-gel polyamic acid 2.0 mmol of 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 5 portions at room temperature and the stirring speed was 400 r/ Stirring under the condition of min for 28 h to obtain a sol-gel polyamic acid;
  • the sol-gel-like polystyrene acid without bubbles is poured onto the substrate, and the temperature is raised from room temperature to 90 ° C at a heating rate of 2 ° C / min, and the temperature is maintained at 90 ° C for 2 h; Then, the temperature was raised to 140 ° C at a heating rate of 2 ° C / min, and the temperature was maintained at 140 ° C for 2 h; then the temperature was raised to 190 ° C at a heating rate of 2 ° C / min, and the temperature was maintained at 190 ° C for 2 h; The heating rate of °C/min is up to 250 °C, and the temperature is kept at 250 °C for 2 h; then the temperature is raised to 290 °C at a heating rate of 2 °C/min, and the temperature is maintained at 290 °C for 2 h; then at 2 °C/min.
  • the heating rate was raised to 340 ° C, and the temperature was maintained at 340 ° C for 2 h; finally, the temperature was lowered from 340 ° C to room temperature at a cooling rate of 2 ° C / min to obtain a substrate of a polyamide film.
  • the substrate of the polyamide film is placed in distilled water to remove the polyamic acid film from the substrate of the polyamide film, and then the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 180 ° C. At 360 min, a high temperature resistant thermoplastic shape memory polyimide was obtained.
  • the weight average molecular weight of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 5 was measured by gel permeation chromatography to be 104.6 kg/mol.
  • thermoplastic shape memory polyimide prepared in Example 5 was measured using a gel permeation chromatograph:
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 5 had a glass transition temperature T g of 319 °C.
  • the storage modulus at room temperature, that is, the glass state at 30 ° C is 2568 MPa; the storage modulus at the high temperature of 339 ° C, that is, T g + 20 ° C in the rubber state is about 8.7 MPa.
  • the decomposition temperature at which the mass loss resistance of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 5 was 5% was 526 ° C, and the residue at 800 ° C was 57.6%.
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 5 was folded 180° on a hot plate at 310 ° C to return to the original shape for 35 s.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)

Abstract

A high temperature-resistant thermoplastic shape-memory polyimide and a preparation method therefor, related to a polyimide and a preparation method therefor. The present invention aims to solve the problem that an existing shape-memory polymer is inapplicable in a high temperature field due to a low glass transition temperature, Tg, and poor thermal properties and thermodynamic properties at high temperatures. The high temperature-resistant thermoplastic shape-memory polyimide is prepared with 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and 4,4'-diaminodiphenylether as reactive monomers and has a structural formula as represented by formula (I). The preparation method: 1. dissolving of 4,4'-diaminodiphenylether monomers; 2. preparation of a sol-gel-like polyamic acid; 3. removal of residual air bubbles; 4. thermal imidization; and, 5. mold releasing. The present invention produces the high temperature-resistant thermoplastic shape-memory polyimide.

Description

一种耐高温热塑性形状记忆聚酰亚胺及其制备方法High temperature resistant thermoplastic shape memory polyimide and preparation method thereof 技术领域Technical field
本发明涉及一种形状记忆聚酰亚胺及其制备方法。The invention relates to a shape memory polyimide and a preparation method thereof.
背景技术Background technique
形状记忆聚合物(shape memory polymer,SMP)是指具有初始形状，在一定条件下经形变并固定后，能够感知并响应外界变化的刺激而恢复其初始状态的高分子材料。现在世界各国已开发出形状记忆聚氨酯、形状记忆聚苯乙烯、形状记忆环氧树脂等多种SMP材料[Nature,2010,464,267-270.]，在智能纺织、生物医疗、航空航天等诸多领域发挥着越来越重要的作用。热塑性SMP具有加工容易、使用方便等优点，具有优良的应用和研究前景。如Hu等利用形状记忆聚氨酯制备了形状记忆纤维，利用这些纤维织成的衣物具有独特的形状记忆效应和防水透湿性[Polymer,2009,50,4424–4428.]。但当前常用SMP的玻璃化转变温度(Tg)大多低于120℃，但在高温领域的应用，如高温下基于SMP的驱动装置、航空航天领域等需要耐高温的SMP，但目前耐高温SMP研究较少。A shape memory polymer (SMP) is a polymer material that has an initial shape and is deformed and fixed under certain conditions, and is capable of sensing and responding to external changes of the stimulus to restore its original state. Nowadays, various SMP materials such as shape memory polyurethane, shape memory polystyrene and shape memory epoxy resin have been developed in the world [Nature, 2010, 464, 267-270.], which are used in many fields such as smart textile, biomedical, aerospace and many other fields. More and more important. Thermoplastic SMP has the advantages of easy processing and convenient use, and has excellent application and research prospects. Shape memory fibers are prepared by using shape memory polyurethane such as Hu, and the clothes woven with these fibers have a unique shape memory effect and waterproof moisture permeability [Polymer, 2009, 50, 4424-4428.]. However, the glass transition temperature (T g ) of commonly used SMPs is mostly lower than 120 ° C, but in high temperature applications, such as SMP-based drives at high temperatures, aerospace applications, etc., which require high temperature resistance, but currently high temperature resistant SMP Less research.
聚酰亚胺(PI)是主链结构单元中含有酰亚胺特征基团的芳杂环聚合物，具有耐高温、耐辐射、机械性能优异，加工途径多样化等优点，已被广泛应用于汽车、微电子、航空航天等领域[聚酰亚胺：化学、结构与性能的关系及材料，科学出版社，2012.09.]。因此，形状记忆热塑性聚酰亚胺在诸多领域有广阔的应用前景。热塑性聚酰亚胺一般是指线形大分子结构的可溶性聚酰亚胺，具有可熔融和可溶解加工性。1982年，美国通用电气公司推出了热塑性聚醚酰亚胺Ultem，其优异的可溶可熔加工性能使其依然有较强的市场竞争能力。1994年，日本三井东压化学公司研制了具有优异耐热性能和可熔融加工性能的热塑性聚醚酰亚胺Aurum，该产品利用挤出方法制备制备的薄膜商品名为Regulus。中科院长春应化所从20世纪60年代就开始了聚酰亚胺的研究，开发出YHPI系列热塑性聚酰亚胺。这些聚酰亚胺有很高的韧性和角质感，可进行模压和注射成型，已广泛用于电绝缘和耐磨材料。上海合成树脂研究所从20世纪70年代以来开发了Ratem系列聚酰亚胺工程塑料，可作为棒材、板材、管材及其加工或烧结零件等应用。2013年Vaia等报道了Tg在220℃附近的热固性聚酰亚胺SMP[Polymer 2013,54,391-402.]。但目前国内外尚无Tg>300℃的SMP的报道。Polyimide (PI) is an aromatic heterocyclic polymer containing an imide characteristic group in the main chain structural unit, and has the advantages of high temperature resistance, radiation resistance, excellent mechanical properties, and diverse processing paths, and has been widely used. Automotive, microelectronics, aerospace and other fields [polyimide: relationship between chemistry, structure and properties and materials, Science Press, 2012.09.]. Therefore, shape memory thermoplastic polyimide has broad application prospects in many fields. Thermoplastic polyimide generally refers to a soluble polyimide having a linear macromolecular structure with meltable and dissolvable processability. In 1982, General Electric Company of the United States introduced the thermoplastic polyetherimide Ultem, which has excellent soluble melt processing properties and still has strong market competitiveness. In 1994, Mitsui Chemicals Co., Ltd. of Japan developed a thermoplastic polyetherimide Aurum with excellent heat resistance and melt processability. The product was prepared by extrusion method and sold under the trade name Regulus. The Changchun Yinghua Institute of the Chinese Academy of Sciences began researching polyimides in the 1960s and developed the YHPI series of thermoplastic polyimides. These polyimides have high toughness and horniness and can be molded and injection molded. They have been widely used in electrical insulation and wear resistant materials. The Shanghai Synthetic Resin Research Institute has developed the Ratem series of polyimide engineering plastics since the 1970s, which can be used as bars, plates, tubes and processed or sintered parts. In 2013, Vaia et al. reported a thermosetting polyimide SMP with a T g around 220 ° C [Polymer 2013, 54, 391-402.]. However, there are no reports of SMP with T g >300 °C at home and abroad.
发明内容Summary of the invention
本发明的目的是要解决现有形状记忆聚合物玻璃化转变温度Tg低，高温下热性能和热力学性能较差，不能在高温领域应用的问题，而提供一种耐高温热塑性形状记忆聚酰亚胺及其制备方法。The object of the present invention is to solve the problem that the existing shape memory polymer has a low glass transition temperature T g , poor thermal properties and thermodynamic properties at high temperatures, and cannot be applied in a high temperature field, and provides a high temperature resistant thermoplastic shape memory polyacyl group. Imine and its preparation method.
一种耐高温热塑性形状记忆聚酰亚胺由4,4'-(六氟异丙烯)二酞酸酐和4,4'-二氨基二苯醚作为反应单体制备而成；所述的4,4'-(六氟异丙烯)二酞酸酐单体与4,4'-二氨基二苯醚单体的物质的量比为1:1。A high temperature resistant thermoplastic shape memory polyimide prepared by using 4,4'-(hexafluoroisopropene) diphthalic anhydride and 4,4'-diaminodiphenyl ether as a reactive monomer; The amount ratio of the 4'-(hexafluoroisopropene) diphthalic anhydride monomer to the 4,4'-diaminodiphenyl ether monomer was 1:1.
一种耐高温热塑性形状记忆聚酰亚胺的结构式为： The structural formula of a high temperature resistant thermoplastic shape memory polyimide is:
Figure PCTCN2015070308-appb-000001
Figure PCTCN2015070308-appb-000001
其中，所述的n的范围为128～172。Wherein, the range of n is from 128 to 172.
一种耐高温热塑性形状记忆聚酰亚胺的制备方法，是按以下步骤完成的：A method for preparing a high temperature resistant thermoplastic shape memory polyimide is accomplished by the following steps:
一、溶解4,4'-二氨基二苯醚单体：将4,4'-二氨基二苯醚单体加入到N,N'-二甲基乙酰胺中，在室温和干燥的氮气气氛下搅拌至4,4'-二氨基二苯醚单体完全溶解，得到二胺溶液；1. Dissolving 4,4'-diaminodiphenyl ether monomer: adding 4,4'-diaminodiphenyl ether monomer to N,N'-dimethylacetamide at room temperature and a dry nitrogen atmosphere Stirring until the 4,4'-diaminodiphenyl ether monomer is completely dissolved to obtain a diamine solution;
步骤一所述的4,4'-二氨基二苯醚单体的物质的量与N,N'-二甲基乙酰胺的体积比为(0.1mmol～0.2mmol):1mL；The volume ratio of the amount of the 4,4'-diaminodiphenyl ether monomer to the N,N'-dimethylacetamide in the first step is (0.1 mmol to 0.2 mmol): 1 mL;
二、制备溶胶凝胶状聚酰胺酸：将4,4'-(六氟异丙烯)二酞酸酐单体分3次～6次加入到二胺溶液中，在室温和搅拌速度为300r/min～400/min的条件下搅拌25h～30h，得到溶胶凝胶状聚酰胺酸；2. Preparation of sol-gel polyamic acid: 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 3 to 6 times at room temperature and stirring speed was 300 r/min. Stirring for 25 to 30 hours under conditions of ~400/min to obtain a sol-gel polyamic acid;
步骤二所述的4,4'-(六氟异丙烯)二酞酸酐单体与二胺溶液中4,4'-二氨基二苯醚单体的物质的量比为1:1；The ratio of the amount of the 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer to the 4,4'-diaminodiphenyl ether monomer in the diamine solution is 1:1;
三、去除残留气泡：将溶胶凝胶状聚酰胺酸在50℃～80℃的真空干燥箱中干燥处理1.5h～2.5h，得到溶胶凝胶状不含气泡的聚酰胺酸；3. Removing residual bubbles: drying the sol-gel polyamic acid in a vacuum oven at 50 ° C to 80 ° C for 1.5 h to 2.5 h to obtain a sol-gel-like polyamic acid containing no bubbles;
四、热酰亚胺化：将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min～2℃/min的升温速率从室温开始升温至60℃～90℃，并在温度为60℃～90℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至120℃～140℃，并在温度为120℃～140℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至170℃～190℃，并在温度为170℃～190℃下保温1h～2h；再以1℃/min～2℃/min的升温速率至220℃～250℃，并在温度为220℃～250℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至270℃～290℃，并在温度为270℃～290℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至320℃～340℃，并在温度为320℃～340℃下保温1h～2h；最后以1℃/min～2℃/min的降温速率从温度为320℃～340℃降温至室温，得到聚酰胺薄膜的基板；4. Thermal imidization: the sol-gel-like polystyrene acid is poured onto the substrate, and the temperature is raised from room temperature to 60 ° C to 90 ° C at a heating rate of 1 ° C / min to 2 ° C / min, and The temperature is maintained at 60 ° C ~ 90 ° C for 1 h ~ 2 h; then at 1 ° C / min ~ 2 ° C / min heating rate to 120 ° C ~ 140 ° C, and at a temperature of 120 ° C ~ 140 ° C for 1 h ~ 2h Then, the temperature is raised to 170 ° C ~ 190 ° C at a heating rate of 1 ° C / min ~ 2 ° C / min, and the temperature is maintained at 170 ° C ~ 190 ° C for 1 h ~ 2 h; and then 1 ° C / min ~ 2 ° C / min The heating rate is up to 220 ° C ~ 250 ° C, and the temperature is maintained at 220 ° C ~ 250 ° C for 1 h ~ 2h; and then heated at a temperature increase rate of 1 ° C / min ~ 2 ° C / min to 270 ° C ~ 290 ° C, and at the temperature The temperature is maintained at 270 ° C ~ 290 ° C for 1 h ~ 2 h; then at a temperature increase rate of 1 ° C / min ~ 2 ° C / min to 320 ° C ~ 340 ° C, and the temperature is maintained at 320 ° C ~ 340 ° C for 1 h ~ 2 h; a cooling rate of 1 ° C / min ~ 2 ° C / min from a temperature of 320 ° C ~ 340 ° C to room temperature to obtain a polyamide film substrate;
五、脱膜：将聚酰胺薄膜的基板置于蒸馏水中，使聚酰胺薄膜从聚酰胺薄膜的基板上脱落，再使用蒸馏水将聚酰胺薄膜冲洗干净，最后在温度为120℃～180℃的条件下加热360min～600min，得到耐高温热塑性形状记忆聚酰亚胺。5. Stripping: The substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally at a temperature of 120 ° C to 180 ° C. The lower temperature is heated for 360 min to 600 min to obtain a high temperature resistant thermoplastic shape memory polyimide.
本发明步骤二中的化学反应式为： The chemical reaction formula in the second step of the present invention is:
Figure PCTCN2015070308-appb-000002
Figure PCTCN2015070308-appb-000002
本发明步骤四中的化学反应式为：The chemical reaction formula in the fourth step of the present invention is:
Figure PCTCN2015070308-appb-000003
Figure PCTCN2015070308-appb-000003
本发明的优点：Advantages of the invention:
一、本发明制备的耐高温热塑性形状记忆聚酰亚胺的玻璃化转变温度Tg为313℃～319℃，使其可应用于高温形状记忆聚合物领域； 1. The high temperature thermoplastic shape memory polyimide prepared by the invention has a glass transition temperature T g of 313 ° C to 319 ° C, which makes it applicable to the field of high temperature shape memory polymers;
二、本发明制备的材料在室温25℃下即可溶解在氯仿、甲苯、二甲苯、N,N'-二甲基乙酰胺等有机溶剂中，具有可进行低温溶剂加工的优异可加工性能；2. The material prepared by the invention can be dissolved in an organic solvent such as chloroform, toluene, xylene or N,N'-dimethylacetamide at room temperature at 25 ° C, and has excellent processability for low-temperature solvent processing;
三、本发明制备的耐高温热塑性形状记忆聚酰亚胺质量损失为5％时的分解温度大于520℃，说明该材料具有在高温下的热稳定性，可在高温环境中长期应用；3. The decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared by the invention is 5% when the mass loss is 5%, which indicates that the material has thermal stability at high temperature and can be used for a long time in a high temperature environment;
四、本发明制备的耐高温热塑性形状记忆聚酰亚胺具有优异的热力学效应，在常温30℃玻璃态时的存储模量大于2GPa；高温(Tg+20℃)橡胶态时的存储模量大于6MPa；保证了该材料在高温下结构件尺寸与形状的稳定性；4. The high temperature resistant thermoplastic shape memory polyimide prepared by the invention has excellent thermodynamic effect, the storage modulus is greater than 2 GPa at a normal temperature of 30 ° C glass state, and the storage modulus at a high temperature (T g + 20 ° C) rubber state. More than 6 MPa; the stability of the size and shape of the structural member at high temperature is ensured;
五、本发明制备的耐高温热塑性形状记忆聚酰亚胺有优异的耐高低温性能，其在-120℃～120℃的温度交替氛围中100h后，其形状记忆性能没有降低。5. The high temperature resistant thermoplastic shape memory polyimide prepared by the invention has excellent high and low temperature resistance, and its shape memory performance is not lowered after being heated for 100 hours in an alternating atmosphere of -120 ° C to 120 ° C.
本发明可获得一种耐高温热塑性形状记忆聚酰亚胺。The present invention provides a high temperature resistant thermoplastic shape memory polyimide.
附图说明DRAWINGS
图1是实施例1制备的耐高温热塑性形状记忆聚酰亚胺的红外光谱图；1 is an infrared spectrum diagram of a high temperature resistant thermoplastic shape memory polyimide prepared in Example 1;
图2是实施例1制备的耐高温热塑性形状记忆聚酰亚胺的损耗因子图；2 is a loss factor diagram of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1;
图3是实施例1制备的耐高温热塑性形状记忆聚酰亚胺的存储模量图；3 is a storage modulus diagram of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1;
图4是实施例1制备的耐高温热塑性形状记忆聚酰亚胺的热失重分析图；4 is a thermogravimetric analysis diagram of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1;
图5是实施例1制备的耐高温热塑性形状记忆聚酰亚胺在310℃下弯曲，室温下固定得到的暂时形状；5 is a temporary shape obtained by bending a high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 at 310 ° C and fixing at room temperature;
图6是实施例1制备的耐高温热塑性形状记忆聚酰亚胺在310℃热台上2s后形状恢复情况；6 is a shape recovery state of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 2 s on a hot stage at 310 ° C;
图7是实施例1制备的耐高温热塑性形状记忆聚酰亚胺在310℃热台上10s后形状恢复情况；7 is a shape recovery state of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 10 s on a hot stage at 310 ° C;
图8是实施例1制备的耐高温热塑性形状记忆聚酰亚胺在310℃热台上13s后形状恢复情况；8 is a shape recovery state of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 13 s on a hot stage at 310 ° C;
图9是实施例1制备的耐高温热塑性形状记忆聚酰亚胺在310℃热台上16s后形状恢复情况；9 is a shape recovery state of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 16 s on a hot stage at 310 ° C;
图10是实施例1制备的耐高温热塑性形状记忆聚酰亚胺在310℃热台上23s后形状恢复其原始形状。Figure 10 is a view showing the shape of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 restored to its original shape after 23 seconds on a hot stage at 310 °C.
具体实施方式detailed description
具体实施方式一：本实施方式是一种耐高温热塑性形状记忆聚酰亚胺由4,4'-(六氟异丙烯)二酞酸酐和4,4'-二氨基二苯醚作为反应单体制备而成；所述的4,4'-(六氟异丙烯)二酞酸酐单体与4,4'-二氨基二苯醚单体的物质的量比为1:1。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment: The present embodiment is a high temperature resistant thermoplastic shape memory polyimide comprising 4,4'-(hexafluoroisopropene) dinonanhydride and 4,4'-diaminodiphenyl ether as a reactive monomer Prepared; the amount ratio of the 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer to the 4,4'-diaminodiphenyl ether monomer is 1:1.
具体实施方式二：本实施方式与具体实施方式一不同的是：一种耐高温热塑性形状记忆聚酰亚胺的结构式为： DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 2: This embodiment differs from the specific embodiment in that the structural formula of a high temperature resistant thermoplastic shape memory polyimide is:
Figure PCTCN2015070308-appb-000004
Figure PCTCN2015070308-appb-000004
其中，所述的n的范围为128～172。其他步骤与具体实施方式一相同。Wherein, the range of n is from 128 to 172. The other steps are the same as in the first embodiment.
具体实施方式三：本实施方式与具体实施方式二不同点是：一种耐高温热塑性形状记忆聚酰亚胺的重均分子量为77.8kg/mol～104.6kg/mol。其他步骤与具体实施方式二相同。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 3: This embodiment differs from the second embodiment in that a high temperature resistant thermoplastic shape memory polyimide has a weight average molecular weight of 77.8 kg/mol to 104.6 kg/mol. The other steps are the same as in the second embodiment.
具体实施方式四：本实施方式与具体实施方式二至三之一不同点是：所述的n的范围为130～170。其他步骤与具体实施方式二至三相同。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 4: This embodiment differs from one of the second to third embodiments in that: the range of n is 130-170. The other steps are the same as the specific embodiments 2-3.
具体实施方式五：本实施方式是一种耐高温热塑性形状记忆聚酰亚胺的制备方法，是按以下步骤完成的：DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS V. This embodiment is a method for preparing a high temperature resistant thermoplastic shape memory polyimide, which is completed as follows:
一、溶解4,4'-二氨基二苯醚单体：将4,4'-二氨基二苯醚单体加入到N,N'-二甲基乙酰胺中，在室温和干燥的氮气气氛下搅拌至4,4'-二氨基二苯醚单体完全溶解，得到二胺溶液；1. Dissolving 4,4'-diaminodiphenyl ether monomer: adding 4,4'-diaminodiphenyl ether monomer to N,N'-dimethylacetamide at room temperature and a dry nitrogen atmosphere Stirring until the 4,4'-diaminodiphenyl ether monomer is completely dissolved to obtain a diamine solution;
步骤一所述的4,4'-二氨基二苯醚单体的物质的量与N,N'-二甲基乙酰胺的体积比为(0.1mmol～0.2mmol):1mL；The volume ratio of the amount of the 4,4'-diaminodiphenyl ether monomer to the N,N'-dimethylacetamide in the first step is (0.1 mmol to 0.2 mmol): 1 mL;
二、制备溶胶凝胶状聚酰胺酸：将4,4'-(六氟异丙烯)二酞酸酐单体分3次～6次加入到二胺溶液中，在室温和搅拌速度为300r/min～400/min的条件下搅拌25h～30h，得到溶胶凝胶状聚酰胺酸；2. Preparation of sol-gel polyamic acid: 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 3 to 6 times at room temperature and stirring speed was 300 r/min. Stirring for 25 to 30 hours under conditions of ~400/min to obtain a sol-gel polyamic acid;
步骤二所述的4,4'-(六氟异丙烯)二酞酸酐单体与二胺溶液中4,4'-二氨基二苯醚单体的物质的量比为1:1；The ratio of the amount of the 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer to the 4,4'-diaminodiphenyl ether monomer in the diamine solution is 1:1;
三、去除残留气泡：将溶胶凝胶状聚酰胺酸在50℃～80℃的真空干燥箱中干燥处理1.5h～2.5h，得到溶胶凝胶状不含气泡的聚酰胺酸；3. Removing residual bubbles: drying the sol-gel polyamic acid in a vacuum oven at 50 ° C to 80 ° C for 1.5 h to 2.5 h to obtain a sol-gel-like polyamic acid containing no bubbles;
四、热酰亚胺化：将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min～2℃/min的升温速率从室温开始升温至60℃～90℃，并在温度为60℃～90℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至120℃～140℃，并在温度为120℃～140℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至170℃～190℃，并在温度为170℃～190℃下保温1h～2h；再以1℃/min～2℃/min的升温速率至220℃～250℃，并在温度为220℃～250℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至270℃～290℃，并在温度为270℃～290℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至320℃～340℃，并在温度为320℃～340℃下保温1h～2h；最后以1℃/min～2℃/min的降温速率从温度为320℃～340℃降温至室温，得到聚酰胺薄膜的基板；4. Thermal imidization: the sol-gel-like polystyrene acid is poured onto the substrate, and the temperature is raised from room temperature to 60 ° C to 90 ° C at a heating rate of 1 ° C / min to 2 ° C / min, and The temperature is maintained at 60 ° C ~ 90 ° C for 1 h ~ 2 h; then at 1 ° C / min ~ 2 ° C / min heating rate to 120 ° C ~ 140 ° C, and at a temperature of 120 ° C ~ 140 ° C for 1 h ~ 2h Then, the temperature is raised to 170 ° C ~ 190 ° C at a heating rate of 1 ° C / min ~ 2 ° C / min, and the temperature is maintained at 170 ° C ~ 190 ° C for 1 h ~ 2 h; and then 1 ° C / min ~ 2 ° C / min The heating rate is up to 220 ° C ~ 250 ° C, and the temperature is maintained at 220 ° C ~ 250 ° C for 1 h ~ 2h; and then heated at a temperature increase rate of 1 ° C / min ~ 2 ° C / min to 270 ° C ~ 290 ° C, and at the temperature The temperature is maintained at 270 ° C ~ 290 ° C for 1 h ~ 2 h; then at a temperature increase rate of 1 ° C / min ~ 2 ° C / min to 320 ° C ~ 340 ° C, and the temperature is maintained at 320 ° C ~ 340 ° C for 1 h ~ 2 h; a cooling rate of 1 ° C / min ~ 2 ° C / min from a temperature of 320 ° C ~ 340 ° C to room temperature to obtain a polyamide film substrate;
五、脱膜：将聚酰胺薄膜的基板置于蒸馏水中，使聚酰胺薄膜从聚酰胺薄膜的基板上脱落，再使用蒸馏水将聚酰胺薄膜冲洗干净，最后在温度为120℃～180℃的条件下加热360min～600min，得到耐高温热塑性形状记忆聚酰亚胺。 5. Stripping: The substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally at a temperature of 120 ° C to 180 ° C. The lower temperature is heated for 360 min to 600 min to obtain a high temperature resistant thermoplastic shape memory polyimide.
本实施方式步骤二中的化学反应式为：The chemical reaction formula in the second step of the present embodiment is:
Figure PCTCN2015070308-appb-000005
Figure PCTCN2015070308-appb-000005
本实施方式步骤四中的化学反应式为：The chemical reaction formula in the fourth step of the present embodiment is:
Figure PCTCN2015070308-appb-000006
Figure PCTCN2015070308-appb-000006
本实施方式的优点：Advantages of this embodiment:
一、本实施方式制备的耐高温热塑性形状记忆聚酰亚胺的玻璃化转变温度Tg为 313℃～319℃，使其可应用于高温形状记忆聚合物领域；1. The high temperature thermoplastic shape memory polyimide prepared by the embodiment has a glass transition temperature T g of 313 ° C to 319 ° C, which can be applied to the field of high temperature shape memory polymers;
二、本实施方式制备的材料在室温25℃下即可溶解在氯仿、甲苯、二甲苯、N,N'-二甲基乙酰胺等有机溶剂中，具有可进行低温溶剂加工的优异可加工性能；2. The material prepared in the present embodiment can be dissolved in an organic solvent such as chloroform, toluene, xylene or N,N'-dimethylacetamide at room temperature at 25 ° C, and has excellent processability for low-temperature solvent processing. ;
三、本实施方式制备的耐高温热塑性形状记忆聚酰亚胺质量损失为5％时的分解温度大于520℃，说明该材料具有在高温下的热稳定性，可在高温环境中长期应用；3. The decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared by the embodiment is 5% when the mass loss is 5%, which indicates that the material has thermal stability at high temperature and can be used for a long time in a high temperature environment;
四、本实施方式制备的耐高温热塑性形状记忆聚酰亚胺具有优异的热力学效应，在常温30℃玻璃态时的存储模量大于2GPa；高温337℃橡胶态时的存储模量大于6MPa；保证了该材料在高温下结构件尺寸与形状的稳定性；Fourth, the high temperature resistant thermoplastic shape memory polyimide prepared by the embodiment has excellent thermodynamic effect, the storage modulus is greater than 2 GPa at a normal temperature of 30 ° C glass state; the storage modulus at a high temperature of 337 ° C rubber state is greater than 6 MPa; The stability of the size and shape of the structural member at high temperatures;
五、本实施方式制备的耐高温热塑性形状记忆聚酰亚胺有优异的耐高低温性能，其在-120℃～120℃的温度交替氛围中100h后，其形状记忆性能没有降低。5. The high temperature resistant thermoplastic shape memory polyimide prepared by the present embodiment has excellent high and low temperature resistance, and its shape memory performance is not lowered after being heated for 100 hours in an alternating atmosphere of -120 ° C to 120 ° C.
本实施方式可获得一种耐高温热塑性形状记忆聚酰亚胺。This embodiment provides a high temperature resistant thermoplastic shape memory polyimide.
具体实施方式六：本实施方式与具体实施方式五不同点是：步骤一所述的4,4'-二氨基二苯醚单体的物质的量与N,N'-二甲基乙酰胺溶剂的体积比为(0.11mmol～0.19mmol):1mL。其他步骤与具体实施方式五相同。BEST MODE FOR CARRYING OUT THE INVENTION Sixth embodiment: The difference between the embodiment and the fifth embodiment is that the amount of the 4,4′-diaminodiphenyl ether monomer in the step 1 is different from the N,N′-dimethylacetamide solvent. The volume ratio was (0.11 mmol to 0.19 mmol): 1 mL. The other steps are the same as in the fifth embodiment.
具体实施方式七：本实施方式与具体实施方式五或六之一不同点是：步骤三中将溶胶凝胶状聚酰胺酸在55℃～75℃的真空干燥箱中干燥处理1.5h～2h，得到溶胶凝胶状不含气泡的聚酰胺酸。其他步骤与具体实施方式五或六相同。Specific Embodiment 7: This embodiment differs from one of the fifth or sixth embodiment in that: in step 3, the sol-gel polyamic acid is dried in a vacuum drying oven at 55 ° C to 75 ° C for 1.5 h to 2 h. A sol-gel-like polyamic acid containing no bubbles was obtained. The other steps are the same as the fifth or sixth embodiment.
具体实施方式八：本实施方式与具体实施方式五至七之一不同点是：步骤四中将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min～2℃/min的升温速率从室温开始升温至70℃～80℃，并在温度为70℃～80℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至130℃～140℃，并在温度为130℃～140℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至170℃～190℃，并在温度为170℃～190℃下保温1h～2h；再以1℃/min～2℃/min的升温速率至220℃～250℃，并在温度为220℃～250℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至270℃～290℃，并在温度为270℃～290℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至320℃～330℃，并在温度为320℃～330℃下保温1h～2h；最后以1℃/min～2℃/min的降温速率从温度为320℃～330℃降温至室温，得到聚酰胺薄膜的基板。其他步骤与具体实施方式五至七相同。BEST MODE 8: This embodiment differs from one of the fifth to seventh embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the sol-gel-like bubble-free is used. The polyamic acid is poured onto the substrate, and the temperature is raised from room temperature to 70 ° C to 80 ° C at a heating rate of 1 ° C / min to 2 ° C / min, and the temperature is maintained at 70 ° C to 80 ° C for 1 h to 2 h; The heating rate of °C/min~2°C/min is raised to 130°C～140°C, and the temperature is maintained at 130°C～140°C for 1h～2h; then the temperature is raised at the heating rate of 1°C/min～2°C/min. 170 ° C ~ 190 ° C, and the temperature is maintained at 170 ° C ~ 190 ° C for 1 h ~ 2h; then at a temperature increase rate of 1 ° C / min ~ 2 ° C / min to 220 ° C ~ 250 ° C, and at a temperature of 220 ° C ~ 250 Incubate at °C for 1h~2h; then raise the temperature to 270°C～290°C at a temperature increase rate of 1°C/min～2°C/min, and keep it at 270°C～290°C for 1h～2h; then 1°C/min The temperature increase rate of ～2°C/min is raised to 320°C～330°C, and the temperature is kept at 320°C～330°C for 1h～2h; finally, the temperature decreasing rate is from 320°C to 1°C/min～2°C/min. ～330°C drop To room temperature to give a polyamide film substrate. The other steps are the same as the specific embodiments five to seven.
具体实施方式九：本实施方式与具体实施方式五至八之一不同点是：步骤四中将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min的升温速率从室温开始升温至60℃，并在温度为60℃下保温2h；再以1℃/min的升温速率升温至120℃，并在温度为120℃下保温1h；再以1℃/min的升温速率升温至170℃，并在温度为170℃下保温1h；再以1℃/min的升温速率至220℃，并在温度为220℃下保温1h；再以1℃/min的升温速率升温至270℃，并在温度为270℃下保温1h；再以1℃/min的升温速率升温至330℃，并在温度为330℃下保温1h；最后以1℃/min的降温速率从温度为330℃降温至室温，得到聚酰胺薄膜的基板。其他步骤与具体实施方式五至八相同。BEST MODE FOR CARRYING OUT THE INVENTION Nine: This embodiment differs from one of the fifth to eighth embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate at a heating rate of 1 ° C/min. The temperature was raised to 60 ° C at room temperature, and the temperature was maintained at 60 ° C for 2 h; then the temperature was raised to 120 ° C at a heating rate of 1 ° C / min, and kept at a temperature of 120 ° C for 1 h; then at a heating rate of 1 ° C / min The temperature is raised to 170 ° C, and the temperature is maintained at 170 ° C for 1 h; then at a temperature increase rate of 1 ° C / min to 220 ° C, and the temperature is maintained at 220 ° C for 1 h; and then heated at a temperature increase rate of 1 ° C / min to 270 °C, and kept at a temperature of 270 ° C for 1 h; then at a temperature increase rate of 1 ° C / min to 330 ° C, and at a temperature of 330 ° C for 1 h; finally at a temperature of 1 ° C / min from the temperature of 330 ° C The substrate was cooled to room temperature to obtain a polyamide film. The other steps are the same as the specific embodiments five to eight.
具体实施方式十：本实施方式与具体实施方式五至九之一不同点是：步骤四中将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min的升温速率从室温开始升温至60℃，并在温度为60℃保温2h；再以1℃/min的升温速率升温至120℃，并在温度为120℃下 保温2h；再以1℃/min的升温速率升温至170℃，并在温度为170℃下保温2h；再以1℃/min的升温速率至220℃，并在温度为220℃下保温2h；再以2℃/min的升温速率升温至270℃，并在温度为270℃下保温1h；再以2℃/min的升温速率升温至330℃，并在温度为330℃下保温1h；最后以2℃/min的降温速率从温度为330℃降温至室温，得到聚酰胺薄膜的基板。其他步骤与具体实施方式五至九相同。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 10: This embodiment differs from one of the fifth to ninth embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate at a heating rate of 1 ° C/min. The temperature was raised to 60 ° C at room temperature, and the temperature was kept at 60 ° C for 2 h; then the temperature was raised to 120 ° C at a heating rate of 1 ° C / min, and the temperature was 120 ° C. Incubate for 2 h; then raise the temperature to 170 ° C at a heating rate of 1 ° C / min, and keep at a temperature of 170 ° C for 2 h; then at a temperature increase rate of 1 ° C / min to 220 ° C, and at a temperature of 220 ° C for 2 h; Then, the temperature was raised to 270 ° C at a heating rate of 2 ° C / min, and the temperature was maintained at 270 ° C for 1 h; then the temperature was raised to 330 ° C at a heating rate of 2 ° C / min, and the temperature was maintained at 330 ° C for 1 h; The temperature drop rate at 2 ° C / min was lowered from room temperature to 330 ° C to room temperature to obtain a substrate of a polyamide film. The other steps are the same as the specific embodiments 5 to 9.
具体实施方式十一：本实施方式与具体实施方式五至十之一不同点是：步骤四中将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min的升温速率从室温开始升温至70℃，并在温度为70℃保温2h；再以1℃/min的升温速率升温至140℃，并在温度为140℃下保温2h；再以1℃/min的升温速率升温至180℃，并在温度为180℃下保温1h；再以2℃/min的升温速率至250℃，并在温度为250℃下保温1h；再以2℃/min的升温速率升温至290℃，并在温度为290℃下保温1h；再以2℃/min的升温速率升温至320℃，并在温度为320℃下保温1h；最后以2℃/min的降温速率从温度为320℃降温至室温，得到聚酰胺薄膜的基板。其他步骤与具体实施方式五至十相同。BEST MODE FOR CARRYING OUT THE INVENTION Eleven: This embodiment differs from one of the fifth to eleventh embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate at a heating rate of 1 ° C/min. The temperature was raised from room temperature to 70 ° C, and the temperature was kept at 70 ° C for 2 h; then the temperature was raised to 140 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 140 ° C for 2 h; then at a heating rate of 1 ° C / min The temperature is raised to 180 ° C, and the temperature is maintained at 180 ° C for 1 h; then at a temperature increase rate of 2 ° C / min to 250 ° C, and the temperature is maintained at 250 ° C for 1 h; and then heated at a rate of 2 ° C / min to 290 °C, and kept at a temperature of 290 ° C for 1 h; then at a temperature increase rate of 2 ° C / min to 320 ° C, and at a temperature of 320 ° C for 1 h; finally at a temperature of 2 ° C / min from 320 ° C The substrate was cooled to room temperature to obtain a polyamide film. The other steps are the same as the specific embodiments 5 to 10.
具体实施方式十二：本实施方式与具体实施方式五至十一之一不同点是：步骤四中将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min的升温速率从室温开始升温至80℃，并在温度为80℃保温2h；再以1℃/min的升温速率升温至130℃，并在温度为130℃下保温2h；再以1℃/min的升温速率升温至180℃，并在温度为180℃下保温2h；再以2℃/min的升温速率至230℃，并在温度为230℃下保温1h；再以2℃/min的升温速率升温至280℃，并在温度为280℃下保温1h；再以2℃/min的升温速率升温至330℃，并在温度为330℃下保温1h；最后以2℃/min的降温速率从温度为330℃降温至室温，得到聚酰胺薄膜的基板。其他步骤与具体实施方式五至十一相同。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 12: This embodiment differs from one of the fifth to eleventh embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 1 ° C/min. The temperature is raised from room temperature to 80 ° C, and the temperature is kept at 80 ° C for 2 h; then the temperature is raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 130 ° C for 2 h; then the temperature is raised at 1 ° C / min The temperature is raised to 180 ° C, and the temperature is maintained at 180 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 230 ° C, and the temperature is maintained at 230 ° C for 1 h; and then heated at a temperature increase rate of 2 ° C / min to 280 ° C, and incubated at 280 ° C for 1 h; then at 2 ° C / min heating rate to 330 ° C, and at a temperature of 330 ° C for 1 h; finally at 2 ° C / min cooling rate from a temperature of 330 The temperature was lowered to room temperature at ° C to obtain a substrate of a polyamide film. The other steps are the same as the specific embodiments 5 to 11.
具体实施方式十三：本实施方式与具体实施方式五至十二之一不同点是：步骤四中将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min的升温速率从室温开始升温至80℃，并在温度为80℃保温2h；再以1℃/min的升温速率升温至130℃，并在温度为130℃下保温2h；再以1℃/min的升温速率升温至180℃，并在温度为180℃下保温2h；再以2℃/min的升温速率至230℃，并在温度为230℃下保温2h；再以2℃/min的升温速率升温至280℃，并在温度为280℃下保温1h；再以2℃/min的升温速率升温至330℃，并在温度为330℃下保温1h；最后以2℃/min的降温速率从温度为330℃降温至室温，得到聚酰胺薄膜的基板。其他步骤与具体实施方式五至十二相同。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 13: This embodiment differs from one of the fifth to twelfth embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 1 ° C/min. The temperature is raised from room temperature to 80 ° C, and the temperature is kept at 80 ° C for 2 h; then the temperature is raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 130 ° C for 2 h; then the temperature is raised at 1 ° C / min The temperature is raised to 180 ° C, and the temperature is maintained at 180 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 230 ° C, and the temperature is maintained at 230 ° C for 2 h; and then heated at a temperature increase rate of 2 ° C / min to 280 ° C, and incubated at 280 ° C for 1 h; then at 2 ° C / min heating rate to 330 ° C, and at a temperature of 330 ° C for 1 h; finally at 2 ° C / min cooling rate from a temperature of 330 The temperature was lowered to room temperature at ° C to obtain a substrate of a polyamide film. The other steps are the same as the specific embodiments 5 to 12.
具体实施方式十四：本实施方式与具体实施方式五至十三之一不同点是：步骤四中将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min的升温速率从室温开始升温至80℃，并在温度为80℃保温2h；再以1℃/min的升温速率升温至130℃，并在温度为130℃下保温2h；再以1℃/min的升温速率升温至180℃，并在温度为180℃下保温2h；再以1℃/min的升温速率至240℃，并在温度为240℃下保温1h；再以1℃/min的升温速率升温至280℃，并在温度为280℃下保温1h；再以1℃/min的升温速率升温至330℃，并在温度为330℃下保温1h；最后以1℃/min的降温速率从温度为330℃降温至室温，得到聚酰胺薄膜的基板。其他步骤与具体实施方式五至十三相同。BEST MODE FOR CARRYING OUT THE INVENTION Fourteenth embodiment: This embodiment differs from one of the fifth to thirteenth embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 1 ° C/min. The temperature is raised from room temperature to 80 ° C, and the temperature is kept at 80 ° C for 2 h; then the temperature is raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 130 ° C for 2 h; then the temperature is raised at 1 ° C / min The temperature is raised to 180 ° C, and the temperature is maintained at 180 ° C for 2 h; then at a temperature increase rate of 1 ° C / min to 240 ° C, and the temperature is maintained at 240 ° C for 1 h; and then heated at a temperature increase rate of 1 ° C / min to 280 ° C, and incubated at a temperature of 280 ° C for 1 h; then at a temperature increase rate of 1 ° C / min to 330 ° C, and at a temperature of 330 ° C for 1 h; finally at a rate of 1 ° C / min from the temperature of 330 The temperature was lowered to room temperature at ° C to obtain a substrate of a polyamide film. The other steps are the same as the specific embodiments 5 to 13.
具体实施方式十五：本实施方式与具体实施方式五至十四之一不同点是：步骤四中将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min的升温速率从室温开始升温至 70℃，并在温度为70℃保温2h；再以1℃/min的升温速率升温至130℃，并在温度为130℃下保温2h；再以1℃/min的升温速率升温至180℃，并在温度为180℃下保温2h；再以2℃/min的升温速率至240℃，并在温度为240℃下保温1h；再以2℃/min的升温速率升温至280℃，并在温度为280℃下保温1h；再以2℃/min的升温速率升温至330℃，并在温度为330℃下保温1h；最后以2℃/min的降温速率从温度为330℃降温至室温，得到聚酰胺薄膜的基板。其他步骤与具体实施方式五至十四相同。BEST MODE FOR CARRYING OUT THE INVENTION Fifteenth Embodiment: This embodiment differs from one of the fifth to fourteenth embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 1 ° C/min. The rate starts to increase from room temperature to 70 ° C, and the temperature is maintained at 70 ° C for 2h; then at a temperature increase rate of 1 ° C / min to 130 ° C, and the temperature is maintained at 130 ° C for 2h; and then heated at a temperature of 1 ° C / min to 180 ° C, And the temperature is maintained at 180 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 240 ° C, and the temperature is maintained at 240 ° C for 1 h; then at a temperature increase rate of 2 ° C / min to 280 ° C, and at the temperature The temperature was kept at 280 ° C for 1 h; the temperature was raised to 330 ° C at a heating rate of 2 ° C / min, and the temperature was maintained at 330 ° C for 1 h; finally, the temperature was lowered from 330 ° C to room temperature at a cooling rate of 2 ° C / min. A substrate for a polyamide film. The other steps are the same as those of the specific embodiments 5 to 14.
具体实施方式十六：本实施方式与具体实施方式五至十五之一不同点是：步骤四中将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min的升温速率从室温开始升温至70℃，并在温度为70℃保温2h；再以1℃/min的升温速率升温至130℃，并在温度为130℃下保温2h；再以1℃/min的升温速率升温至180℃，并在温度为180℃下保温2h；再以2℃/min的升温速率至240℃，并在温度为240℃下保温1h；再以2℃/min的升温速率升温至280℃，并在温度为280℃下保温1h；再以2℃/min的升温速率升温至330℃，并在温度为330℃下保温1h；最后以2℃/min的降温速率从温度为330℃降温至室温，得到聚酰胺薄膜的基板。其他步骤与具体实施方式五至十五相同。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Sixteenth embodiment: This embodiment differs from one of the fifth to fifteenth embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 1 ° C/min. The temperature is raised from room temperature to 70 ° C, and the temperature is kept at 70 ° C for 2 h; then the temperature is raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 130 ° C for 2 h; then the temperature is raised at 1 ° C / min The temperature is raised to 180 ° C, and the temperature is maintained at 180 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 240 ° C, and the temperature is maintained at 240 ° C for 1 h; and then heated at a temperature increase rate of 2 ° C / min to 280 ° C, and incubated at 280 ° C for 1 h; then at 2 ° C / min heating rate to 330 ° C, and at a temperature of 330 ° C for 1 h; finally at 2 ° C / min cooling rate from a temperature of 330 The temperature was lowered to room temperature at ° C to obtain a substrate of a polyamide film. The other steps are the same as the specific embodiments 5 to 15.
具体实施方式十七：本实施方式与具体实施方式五至十六一不同点是：步骤四中将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min的升温速率从室温开始升温至80℃，并在温度为80℃保温2h；再以1℃/min的升温速率升温至140℃，并在温度为140℃下保温2h；再以1℃/min的升温速率升温至190℃，并在温度为190℃下保温2h；再以2℃/min的升温速率至250℃，并在温度为250℃下保温1h；再以2℃/min的升温速率升温至290℃，并在温度为290℃下保温2h；再以2℃/min的升温速率升温至340℃，并在温度为340℃下保温2h；最后以2℃/min的降温速率从温度为340℃降温至室温，得到聚酰胺薄膜的基板。其他步骤与具体实施方式五至十六相同。BEST MODE FOR CARRYING OUT THE INVENTION Seventeenth embodiment: This embodiment differs from the specific embodiment five to sixteen one in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate at a heating rate of 1 ° C/min. The temperature was raised from room temperature to 80 ° C, and the temperature was kept at 80 ° C for 2 h; then the temperature was raised to 140 ° C at a heating rate of 1 ° C / min, and kept at a temperature of 140 ° C for 2 h; and then at a heating rate of 1 ° C / min The temperature is raised to 190 ° C, and the temperature is maintained at 190 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 250 ° C, and the temperature is maintained at 250 ° C for 1 h; and then heated at a temperature increase rate of 2 ° C / min to 290 °C, and kept at a temperature of 290 ° C for 2h; then heated to 340 ° C at a temperature increase rate of 2 ° C / min, and incubated at a temperature of 340 ° C for 2 h; finally at a temperature drop of 2 ° C / min from a temperature of 340 ° C The substrate was cooled to room temperature to obtain a polyamide film. The other steps are the same as the specific embodiments 5 to 16.
具体实施方式十八：本实施方式与具体实施方式五至十七之一不同点是：步骤四中将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以2℃/min的升温速率从室温开始升温至90℃，并在温度为90℃保温2h；再以2℃/min的升温速率升温至140℃，并在温度为140℃下保温2h；再以2℃/min的升温速率升温至190℃，并在温度为190℃下保温2h；再以2℃/min的升温速率至250℃，并在温度为250℃下保温2h；再以2℃/min的升温速率升温至290℃，并在温度为290℃下保温2h；再以2℃/min的升温速率升温至340℃，并在温度为340℃下保温2h；最后以2℃/min的降温速率从温度为340℃降温至室温，得到聚酰胺薄膜的基板。其他步骤与具体实施方式五至十七相同。BEST MODE FOR CARRYING OUT THE INVENTION Eighteenth: This embodiment differs from one of the fifth to seventeenth embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 2 ° C/min. The temperature is raised from room temperature to 90 ° C, and the temperature is maintained at 90 ° C for 2 h; then the temperature is raised to 140 ° C at a temperature increase rate of 2 ° C / min, and the temperature is maintained at 140 ° C for 2 h; then the temperature is raised at 2 ° C / min The temperature is raised to 190 ° C, and the temperature is maintained at 190 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 250 ° C, and the temperature is maintained at 250 ° C for 2 h; and then heated at a temperature increase rate of 2 ° C / min to 290 ° C, and incubated at a temperature of 290 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 340 ° C, and at a temperature of 340 ° C for 2 h; finally at a rate of 2 ° C / min from the temperature of 340 The temperature was lowered to room temperature at ° C to obtain a substrate of a polyamide film. The other steps are the same as the specific embodiments 5 to 17.
具体实施方式十九：本实施方式与具体实施方式五至十八之一不同点是：步骤一所述的4,4'-二氨基二苯醚单体的物质的量与N,N'-二甲基乙酰胺溶剂的体积比为0.12mmol:1mL。其他步骤与具体实施方式五至十八相同。BEST MODE FOR CARRYING OUT THE INVENTION Nineteen: The difference between this embodiment and one of the fifth to eighteen embodiments is that the amount of the substance of the 4,4'-diaminodiphenyl ether monomer described in the first step is N, N'- The volume ratio of the dimethylacetamide solvent was 0.12 mmol: 1 mL. The other steps are the same as the specific embodiments 5 to 18.
具体实施方式二十：本实施方式与具体实施方式五至十九之一不同点是：步骤一所述的4,4'-二氨基二苯醚单体的物质的量与N,N'-二甲基乙酰胺溶剂的体积比为0.1mmol:1mL。其他步骤与具体实施方式五至十九相同。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 20: This embodiment differs from one of the fifth to nineteenth embodiments in the specific embodiment in that the amount of the substance of the 4,4'-diaminodiphenyl ether monomer described in the first step is N, N'- The volume ratio of the dimethylacetamide solvent was 0.1 mmol: 1 mL. The other steps are the same as the specific embodiments 5 to 19.
具体实施方式二十一：本实施方式与具体实施方式六至二十之一不同点是：步骤一所述的4,4'-二氨基二苯醚单体的物质的量与N,N'-二甲基乙酰胺溶剂的体积比为0.14mmol:1mL。其他步骤与具体实施方式六至二十相同。 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 21: This embodiment differs from the specific embodiment 6 to 21 in that the amount of the 4,4'-diaminodiphenyl ether monomer in step 1 is N, N' The volume ratio of the dimethylacetamide solvent was 0.14 mmol: 1 mL. The other steps are the same as the specific embodiments 6 to 20.
具体实施方式二十二：本实施方式与具体实施方式五至二十一之一不同点是：步骤一所述的4,4'-二氨基二苯醚单体的物质的量与N,N'-二甲基乙酰胺溶剂的体积比为0.15mmol:1mL。其他步骤与具体实施方式五至二十一相同。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Twenty-two: This embodiment differs from one of the fifth to twenty-first embodiments in the following manner: the amount of the substance of the 4,4'-diaminodiphenyl ether monomer described in the first step is N, N. The volume ratio of '-dimethylacetamide solvent was 0.15 mmol: 1 mL. The other steps are the same as the specific embodiments 5 to 21.
具体实施方式二十三：本实施方式与具体实施方式五至二十二之一不同点是：步骤一所述的4,4'-二氨基二苯醚单体的物质的量与N,N'-二甲基乙酰胺溶剂的体积比为0.16mmol:1mL。其他步骤与具体实施方式五至二十二相同。BEST MODE FOR CARRYING OUT THE INVENTION Twenty-three: The difference between this embodiment and one of the fifth to twenty-two embodiments is that the amount of the substance of the 4,4'-diaminodiphenyl ether monomer described in the first step is N, N. The volume ratio of the '-dimethylacetamide solvent was 0.16 mmol: 1 mL. The other steps are the same as the specific embodiments 5 to 22.
具体实施方式二十四：本实施方式与具体实施方式五至二十三之一不同点是：步骤一所述的4,4'-二氨基二苯醚单体的物质的量与N,N'-二甲基乙酰胺溶剂的体积比为0.17mmol:1mL。其他步骤与具体实施方式五至二十三相同。BEST MODE FOR CARRYING OUT THE INVENTION Twenty-four: The difference between this embodiment and one of the fifth to twenty-third embodiments is that the amount of the substance of the 4,4'-diaminodiphenyl ether monomer described in the first step is N, N. The volume ratio of '-dimethylacetamide solvent was 0.17 mmol: 1 mL. The other steps are the same as the specific embodiments 5 to 23.
具体实施方式二十五：本实施方式与具体实施方式五至二十四之一不同点是：步骤一所述的4,4'-二氨基二苯醚单体的物质的量与N,N'-二甲基乙酰胺溶剂的体积比为0.18mmol:1mL。其他步骤与具体实施方式五至二十四相同。BEST MODE FOR CARRYING OUT THE INVENTION Twenty-fifth: This embodiment differs from one of the fifth to twenty-fourth embodiments in the specific embodiment in that the amount of the substance of the 4,4'-diaminodiphenyl ether monomer described in the first step is N, N. The volume ratio of the '-dimethylacetamide solvent was 0.18 mmol: 1 mL. The other steps are the same as the specific embodiments 5 to 24.
具体实施方式二十六：本实施方式与具体实施方式五至二十五之一不同点是：步骤一所述的4,4'-二氨基二苯醚单体的物质的量与N,N'-二甲基乙酰胺溶剂的体积比为0.19mmol:1mL。其他步骤与具体实施方式五至二十五相同。BEST MODE FOR CARRYING OUT THE INVENTION Twenty-six: The difference between this embodiment and one of the fifth to twenty-fifth embodiments is that the amount of the substance of the 4,4'-diaminodiphenyl ether monomer described in the first step is N, N. The volume ratio of '-dimethylacetamide solvent was 0.19 mmol: 1 mL. The other steps are the same as the specific embodiments 5 to 25.
具体实施方式二十七：本实施方式与具体实施方式五至二十六之一不同点是：步骤一所述的4,4'-二氨基二苯醚单体的物质的量与N,N'-二甲基乙酰胺溶剂的体积比为0.20mmol:1mL。其他步骤与具体实施方式五至二十六相同。BEST MODE FOR CARRYING OUT THE INVENTION Twenty-seventh: The difference between this embodiment and one of the fifth to twenty-sixth embodiments is that the amount of the substance of the 4,4'-diaminodiphenyl ether monomer described in the first step is N, N. The volume ratio of '-dimethylacetamide solvent was 0.20 mmol: 1 mL. The other steps are the same as the specific embodiments five to twenty-six.
具体实施方式二十八：本实施方式与具体实施方式五至二十七之一不同点是：步骤五中将聚酰胺薄膜的基板置于蒸馏水中，使聚酰胺薄膜从聚酰胺薄膜的基板上脱落，再使用蒸馏水将聚酰胺薄膜冲洗干净，最后在温度为130℃～170℃的条件下加热450min～550min，得到耐高温热塑性形状记忆聚酰亚胺。其他步骤与具体实施方式五至二十七相同。BEST MODE FOR CARRYING OUT THE INVENTION Twenty-eighth: This embodiment differs from one of the fifth to twenty-seventh embodiments in that: in step 5, the substrate of the polyamide film is placed in distilled water to make the polyamide film from the substrate of the polyamide film. After falling off, the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 130 ° C to 170 ° C for 450 min to 550 min to obtain a high temperature resistant thermoplastic shape memory polyimide. The other steps are the same as the specific embodiments 5 to 27.
实施例：Example:
下面参照附图详细描述本发明的实施方式。Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
实施例1：一种耐高温热塑性形状记忆聚酰亚胺的制备方法，是按以下步骤完成的：Example 1: A method for preparing a high temperature resistant thermoplastic shape memory polyimide was carried out by the following steps:
一、溶解4,4'-二氨基二苯醚单体：将1.9mmol 4,4'-二氨基二苯醚单体加入到10mLN,N'-二甲基乙酰胺中，在室温和干燥的氮气气氛下搅拌至4,4'-二氨基二苯醚单体完全溶解，得到二胺溶液；1. Dissolving 4,4'-diaminodiphenyl ether monomer: Add 1.9 mmol of 4,4'-diaminodiphenyl ether monomer to 10 mL of N,N'-dimethylacetamide at room temperature and dry Stirring under nitrogen atmosphere until the 4,4'-diaminodiphenyl ether monomer is completely dissolved to obtain a diamine solution;
二、制备溶胶凝胶状聚酰胺酸：将1.9mmol 4,4'-(六氟异丙烯)二酞酸酐单体分5次加入到二胺溶液中，在室温条件下和搅拌速度为400r/min的条件下搅拌28h，得到溶胶凝胶状聚酰胺酸；2. Preparation of sol-gel polyamic acid: 1.9 mmol of 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 5 portions at room temperature and the stirring speed was 400 r / Stirring under the condition of min for 28 h to obtain a sol-gel polyamic acid;
三、去除残留气泡：将溶胶凝胶状聚酰胺酸在80℃的真空干燥箱中干燥处理1.5h，得到溶胶凝胶状不含气泡的聚酰胺酸；3. Removing residual bubbles: drying the sol-gel polyamic acid in a vacuum oven at 80 ° C for 1.5 h to obtain a sol-gel-like polystyrene containing no bubbles;
四、热酰亚胺化：将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min的升温速率从室温开始升温至80℃，并在温度为80℃保温2h；再以1℃/min的升温速率升温至140℃，并在温度为140℃下保温2h；再以1℃/min的升温速率升温至190℃，并在温度为190℃下保温2h；以2℃/min的升温速率至250℃，并在温度为250℃下保温1h；再以2℃/min的升温速率升温至290℃，并在温度为290℃下保温2h；再以2℃/min的升温速率升温至340℃，并在温度为340℃下保温2h；最后以2℃/min的降温速率从温度为340℃ 降温至室温，得到聚酰胺薄膜的基板。4, thermal imidization: the sol-gel-like polystyrene acid is poured onto the substrate, the temperature is raised from room temperature to 80 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 80 ° C for 2 h; Then, the temperature was raised to 140 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 140 ° C for 2 h; then the temperature was raised to 190 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 190 ° C for 2 h; The heating rate of °C/min is up to 250 °C, and the temperature is maintained at 250 ° C for 1 h; then the temperature is raised to 290 ° C at a heating rate of 2 ° C / min, and the temperature is maintained at 290 ° C for 2 h; then 2 ° C / min The heating rate is raised to 340 ° C, and the temperature is kept at 340 ° C for 2 h; finally, the temperature is 340 ° C at a cooling rate of 2 ° C / min. The substrate was cooled to room temperature to obtain a polyamide film.
五、脱膜：将聚酰胺薄膜的基板置于蒸馏水中，使聚酰胺薄膜从聚酰胺薄膜的基板上脱落，再使用蒸馏水将聚酰胺薄膜冲洗干净，最后在温度为120℃的条件下加热500min，得到耐高温热塑性形状记忆聚酰亚胺。5. Stripping: The substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 120 ° C for 500 min. A high temperature resistant thermoplastic shape memory polyimide is obtained.
实施例1步骤二中的化学反应式为：The chemical reaction formula in the second step of Example 1 is:
Figure PCTCN2015070308-appb-000007
Figure PCTCN2015070308-appb-000007
实施例1步骤四中的化学反应式为： The chemical reaction formula in the fourth step of Example 1 is:
Figure PCTCN2015070308-appb-000008
Figure PCTCN2015070308-appb-000008
使用凝胶渗透色谱仪测得实施例1制备的耐高温热塑性形状记忆聚酰亚胺的重均分子量为101kg/mol。The high temperature thermoplastic shape memory polyimide prepared in Example 1 was measured by gel permeation chromatography to have a weight average molecular weight of 101 kg/mol.
使用凝胶渗透色谱仪测得实施例1制备的耐高温热塑性形状记忆聚酰亚胺的结构式为：The structural formula of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 was measured by gel permeation chromatography:
Figure PCTCN2015070308-appb-000009
Figure PCTCN2015070308-appb-000009
使用红外光谱仪对实施例1制备的耐高温热塑性形状记忆聚酰亚胺进行测试，如图1所示，图1是实施例1制备的耐高温热塑性形状记忆聚酰亚胺的红外光谱图；从图1中可以看出，在1785cm-1处的吸收峰是酰亚胺羰基的不对称伸缩吸收峰(vas C＝O)，而在1723cm-1处的吸收峰为酰亚胺羰基的特征对称伸缩振动峰(vs C＝O)，在1382cm-1为C-N键的伸缩振动吸收峰(vC-N)，在1110cm-1是酰亚胺环的弯曲振动吸收峰(vC-O)。这些特征吸收峰说明实施例1制备的耐高温热塑性形状记忆聚酰亚胺为高度酰亚胺化的聚酰亚胺。The high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 was tested using an infrared spectrometer as shown in FIG. 1. FIG. 1 is an infrared spectrum diagram of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1. As can be seen in Fig. 1, the absorption peak at 1785 cm -1 is the asymmetric stretching peak of imide carbonyl (v as C=O ), and the absorption peak at 1723 cm -1 is characteristic of imide carbonyl. symmetric stretching vibration peak (v s C = O), an absorption peak at 1382cm -1 (V CN) CN bond stretching vibration at 1110cm -1 imide ring was bending vibration absorption peaks (v CO). These characteristic absorption peaks indicate that the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 is a highly imidized polyimide.
使用动态力学分析仪对实施例1制备的耐高温热塑性形状记忆聚酰亚胺进行测试，如图2所示；图2是实施例1制备的耐高温热塑性形状记忆聚酰亚胺的损耗因子图。从图2可知，实施例1制备的耐高温热塑性形状记忆聚酰亚胺的玻璃化转变温度Tg为317℃，由此可知，实施例1制备的耐高温热塑性形状记忆聚酰亚胺可以应用到高温领域。The high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 was tested using a dynamic mechanical analyzer as shown in FIG. 2; FIG. 2 is a loss factor diagram of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1. . It can be seen from FIG. 2 that the glass transition temperature T g of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 is 317 ° C, and thus it can be seen that the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 can be applied. To the high temperature field.
使用动态力学分析仪对实施例1制备的耐高温热塑性形状记忆聚酰亚胺进行测试，如图3所示；图3是耐高温热塑性形状记忆聚酰亚胺的存储模量图；从图3可知，模量变化曲线出现了高、低温度段的两个平台，常温即30℃下玻璃态时的存储模量为2243MPa； 高温337℃即Tg+20℃时橡胶态时的存储模量约为9.7MPa；在两个平台之间存储模量急剧下降，对应于实施例1制备的耐高温热塑性形状记忆聚酰亚胺的玻璃化转变过程，这种模量的急剧变化是聚合物具备形状记忆性质的必要条件。转变中在287℃即Tg-30℃时对应的存储模量为1142MPa，保证实施例1到的耐高温热塑性形状记忆聚酰亚胺作为结构材料使用时，相对目前常用SMP材料在更高的使用温度范围内模量变化相对较小，保证实施例1制备的耐高温热塑性形状记忆聚酰亚胺作为结构件时，尺寸与形状的稳定性。The high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 was tested using a dynamic mechanical analyzer, as shown in FIG. 3; FIG. 3 is a storage modulus diagram of the high temperature resistant thermoplastic shape memory polyimide; It can be seen that the modulus change curve shows two platforms in the high and low temperature sections, and the storage modulus at room temperature, that is, the glass state at 30 ° C is 2243 MPa; the storage modulus at the high temperature of 337 ° C, that is, the rubber state at T g + 20 ° C About 9.7 MPa; the storage modulus drops sharply between the two platforms, corresponding to the glass transition process of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1, the sharp change of the modulus is the polymer The necessary conditions for shape memory properties. The corresponding storage modulus at 287 ° C, ie T g -30 ° C, is 1142 MPa, which ensures that the high temperature resistant thermoplastic shape memory polyimide of Example 1 is used as a structural material, which is higher than the current SMP materials. The change in modulus within the use temperature range is relatively small, and the dimensional and shape stability of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 as a structural member is ensured.
使用热重分析仪对实施例1制备的耐高温热塑性形状记忆聚酰亚胺进行测试，如图4所示；图4是耐高温热塑性形状记忆聚酰亚胺的热失重分析图。从图4可知，实施例1制备的耐高温热塑性形状记忆聚酰亚胺质量损失为5％时的分解温度为525℃，在800℃下的残留为56.2％，说明实施例1制备的耐高温热塑性形状记忆聚酰亚胺具有优良的耐热性能。The high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 was tested using a thermogravimetric analyzer as shown in FIG. 4; and FIG. 4 is a thermogravimetric analysis diagram of the high temperature resistant thermoplastic shape memory polyimide. 4, the decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 was 525 ° C when the mass loss was 5%, and the residual temperature at 800 ° C was 56.2%, indicating the high temperature resistance prepared in Example 1. Thermoplastic shape memory polyimides have excellent heat resistance.
使用高温热台对实施例1制备的耐高温热塑性形状记忆聚酰亚胺进行测试，如图5至图10所示；图5是实施例1制备的耐高温热塑性形状记忆聚酰亚胺在310℃下弯曲，室温下固定制备的暂时形状；图6是实施例1制备的耐高温热塑性形状记忆聚酰亚胺在310℃热台上2s后形状恢复情况；图7是实施例1制备的耐高温热塑性形状记忆聚酰亚胺在310℃热台上10s后形状恢复情况；图8是实施例1制备的耐高温热塑性形状记忆聚酰亚胺在310℃热台上13s后形状恢复情况；图9是实施例1制备的耐高温热塑性形状记忆聚酰亚胺在310℃热台上16s后形状恢复情况；图10是实施例1制备的耐高温热塑性形状记忆聚酰亚胺在310℃热台上23s后形状恢复其原始形状。从图5至图10可知，实施例1制备的耐高温热塑性形状记忆聚酰亚胺具有较好的形状记忆效应。The high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 was tested using a high temperature hot stage, as shown in FIGS. 5 to 10; FIG. 5 is a high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 at 310. The temporary shape prepared by bending at ° C and fixed at room temperature; FIG. 6 is the shape recovery of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 2 s on a hot stage at 310 ° C; FIG. 7 is the resistance of Example 1 The shape recovery of the high temperature thermoplastic shape memory polyimide after 10s on the hot stage at 310 ° C; FIG. 8 is the shape recovery of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 13s on the hot stage at 310 ° C; 9 is the shape recovery of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 16 s on a hot stage at 310 ° C; FIG. 10 is a hot stage of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 at 310 ° C. The shape returns to its original shape after 23s. 5 to 10, the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 has a good shape memory effect.
实施例2：一种耐高温热塑性形状记忆聚酰亚胺的制备方法，是按以下步骤完成的：Example 2: A method for preparing a high temperature resistant thermoplastic shape memory polyimide was carried out by the following steps:
一、溶解4,4'-二氨基二苯醚单体：将1mmol 4,4'-二氨基二苯醚单体加入到10mL N,N'-二甲基乙酰胺中，在室温和干燥的氮气气氛下搅拌至4,4'-二氨基二苯醚单体完全溶解，得到二胺溶液；1. Dissolving 4,4'-diaminodiphenyl ether monomer: Add 1 mmol of 4,4'-diaminodiphenyl ether monomer to 10 mL of N,N'-dimethylacetamide at room temperature and dry Stirring under nitrogen atmosphere until the 4,4'-diaminodiphenyl ether monomer is completely dissolved to obtain a diamine solution;
二、制备溶胶凝胶状聚酰胺酸：将1mmol 4,4'-(六氟异丙烯)二酞酸酐单体分4次加入到二胺溶液中，在室温条件下和搅拌速度为300r/min的条件下搅拌26h，得到溶胶凝胶状聚酰胺酸；2. Preparation of sol-gel polyamic acid: 1 mmol of 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 4 portions at room temperature and the stirring speed was 300 r/min. Stirring under the conditions of 26 h to obtain a sol-gel polyamic acid;
三、去除残留气泡：将溶胶凝胶状聚酰胺酸在50℃的真空干燥箱中干燥处理1.5h，得到溶胶凝胶状不含气泡的聚酰胺酸；3. Removing the residual bubbles: drying the sol-gel polyamic acid in a vacuum oven at 50 ° C for 1.5 h to obtain a sol-gel-like polystyrene containing no bubbles;
四、热酰亚胺化：将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min的升温速率从室温开始升温至70℃，并在温度为70℃保温2h；再以1℃/min的升温速率升温至140℃，并在温度为140℃下保温2h；再以1℃/min的升温速率升温至180℃，并在温度为180℃下保温1h；以2℃/min的升温速率至250℃，并在温度为250℃下保温1h；再以2℃/min的升温速率升温至290℃，并在温度为290℃下保温1h；再以2℃/min的升温速率升温至320℃，并在温度为320℃下保温1h；最后以2℃/min的降温速率从温度为320℃降温至室温，得到聚酰胺薄膜的基板。4, thermal imidization: the sol-gel-like polystyrene acid is poured onto the substrate, the temperature is raised from room temperature to 70 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 70 ° C for 2 h; Then, the temperature was raised to 140 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 140 ° C for 2 h; then the temperature was raised to 180 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 180 ° C for 1 h; The heating rate of °C/min is up to 250 °C, and the temperature is maintained at 250 ° C for 1 h; then the temperature is raised to 290 ° C at a heating rate of 2 ° C / min, and the temperature is maintained at 290 ° C for 1 h; then 2 ° C / min The heating rate was raised to 320 ° C, and the temperature was kept at 320 ° C for 1 h; finally, the temperature was lowered from 320 ° C to room temperature at a cooling rate of 2 ° C / min to obtain a substrate of a polyamide film.
五、脱膜：将聚酰胺薄膜的基板置于蒸馏水中，使聚酰胺薄膜从聚酰胺薄膜的基板上脱落，再使用蒸馏水将聚酰胺薄膜冲洗干净，最后在温度为180℃的条件下加热400min，得到耐高温热塑性形状记忆聚酰亚胺。 5. Stripping: The substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 180 ° C for 400 min. A high temperature resistant thermoplastic shape memory polyimide is obtained.
使用凝胶渗透色谱仪测得实施例2制备的耐高温热塑性形状记忆聚酰亚胺的重均分子量为77.8kg/mol。The weight average molecular weight of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 2 was measured by gel permeation chromatography to be 77.8 kg/mol.
使用凝胶渗透色谱仪测得实施例2制备的耐高温热塑性形状记忆聚酰亚胺的结构式为：The structural formula of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 2 was measured using a gel permeation chromatograph:
Figure PCTCN2015070308-appb-000010
Figure PCTCN2015070308-appb-000010
实施例2制备的耐高温热塑性形状记忆聚酰亚胺的玻璃化转变温度Tg为313℃。常温即30℃下玻璃态时的存储模量为2012MPa；高温333℃即Tg+20℃时橡胶态时的存储模量约为6.2MPa。实施例2制备的耐高温热塑性形状记忆聚酰亚胺质量损失为5％时的分解温度为522℃，在800℃下的残留为53.5％。实施例2制备的耐高温热塑性形状记忆聚酰亚胺在310℃热台上折叠180°回复到原始形状历时33s。The glass transition temperature T g of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 2 was 313 °C. The storage modulus at a normal temperature of 30 ° C in a glass state is 2012 MPa; the storage modulus at a high temperature of 333 ° C, that is, T g + 20 ° C in a rubber state is about 6.2 MPa. The decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 2 at a mass loss of 5% was 522 ° C, and the residue at 800 ° C was 53.5%. The high temperature resistant thermoplastic shape memory polyimide prepared in Example 2 was folded 180° on a hot plate at 310 ° C to return to the original shape for 33 s.
实施例3：一种耐高温热塑性形状记忆聚酰亚胺的制备方法，是按以下步骤完成的：Example 3: A method for preparing a high temperature resistant thermoplastic shape memory polyimide was carried out by the following steps:
一、溶解4,4'-二氨基二苯醚单体：将1.5mmol 4,4'-二氨基二苯醚单体加入到10mLN,N'-二甲基乙酰胺中，在室温和干燥的氮气气氛下搅拌至4,4'-二氨基二苯醚单体完全溶解，得到二胺溶液；1. Dissolving 4,4'-diaminodiphenyl ether monomer: 1.5 mmol of 4,4'-diaminodiphenyl ether monomer was added to 10 mL of N,N'-dimethylacetamide at room temperature and dried. Stirring under nitrogen atmosphere until the 4,4'-diaminodiphenyl ether monomer is completely dissolved to obtain a diamine solution;
二、制备溶胶凝胶状聚酰胺酸：将1.5mmol 4,4'-(六氟异丙烯)二酞酸酐单体分5次加入到二胺溶液中，在室温条件下和搅拌速度为350r/min的条件下搅拌26h，得到溶胶凝胶状聚酰胺酸；2. Preparation of sol-gel polyamic acid: 1.5 mmol of 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 5 portions at room temperature and the stirring speed was 350 r / Stirring under the condition of min for 26 h to obtain a sol-gel polyamic acid;
三、去除残留气泡：将溶胶凝胶状聚酰胺酸在60℃的真空干燥箱中干燥处理2h，得到溶胶凝胶状不含气泡的聚酰胺酸；3. Removing residual bubbles: drying the sol-gel polyamic acid in a vacuum oven at 60 ° C for 2 h to obtain a sol-gel-like polystyrene containing no bubbles;
四、热酰亚胺化：将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min的升温速率从室温开始升温至80℃，并在温度为80℃保温2h；再以1℃/min的升温速率升温至130℃，并在温度为130℃下保温2h；再以1℃/min的升温速率升温至180℃，并在温度为180℃下保温2h；以2℃/min的升温速率至230℃，并在温度为230℃下保温2h；再以2℃/min的升温速率升温至280℃，并在温度为280℃下保温1h；再以2℃/min的升温速率升温至330℃，并在温度为330℃下保温1h；最后以2℃/min的降温速率从温度为330℃降温至室温，得到聚酰胺薄膜的基板。4, thermal imidization: the sol-gel-like polystyrene acid is poured onto the substrate, the temperature is raised from room temperature to 80 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 80 ° C for 2 h; Then, the temperature was raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 130 ° C for 2 h; then the temperature was raised to 180 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 180 ° C for 2 h; The heating rate of °C/min is up to 230 °C, and the temperature is kept at 230 °C for 2 h; then the temperature is raised to 280 °C at a heating rate of 2 °C/min, and the temperature is maintained at 280 °C for 1 h; then at 2 °C/min. The heating rate was raised to 330 ° C, and the temperature was maintained at 330 ° C for 1 h; finally, the temperature was lowered from 330 ° C to room temperature at a cooling rate of 2 ° C / min to obtain a substrate of a polyamide film.
五、脱膜：将聚酰胺薄膜的基板置于蒸馏水中，使聚酰胺薄膜从聚酰胺薄膜的基板上脱落，再使用蒸馏水将聚酰胺薄膜冲洗干净，最后在温度为180℃的条件下加热360min，得到耐高温热塑性形状记忆聚酰亚胺。5. Stripping: The substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 180 ° C for 360 min. A high temperature resistant thermoplastic shape memory polyimide is obtained.
使用凝胶渗透色谱仪测得实施例3制备的耐高温热塑性形状记忆聚酰亚胺的重均分子量为88.8kg/mol。The weight average molecular weight of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 3 was measured by gel permeation chromatography to be 88.8 kg/mol.
使用凝胶渗透色谱仪测得实施例3制备的耐高温热塑性形状记忆聚酰亚胺的结构式为： The structural formula of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 3 was measured using a gel permeation chromatograph:
Figure PCTCN2015070308-appb-000011
Figure PCTCN2015070308-appb-000011
实施例3制备的耐高温热塑性形状记忆聚酰亚胺的玻璃化转变温度Tg为314℃。常温即30℃下玻璃态时的存储模量为2126MPa；高温334℃即Tg+20℃时橡胶态时的存储模量约为7.1MPa。实施例3制备的耐高温热塑性形状记忆聚酰亚胺质量损失为5％时的分解温度为524℃，在800℃下的残留为54.5％。实施例3制备的耐高温热塑性形状记忆聚酰亚胺在310℃热台上折叠180°回复到原始形状历时31s。The high temperature resistant thermoplastic shape memory polyimide prepared in Example 3 had a glass transition temperature Tg of 314 °C. The storage modulus at room temperature, that is, the glass state at 30 ° C is 2126 MPa; the storage modulus at the high temperature of 334 ° C, that is, T g + 20 ° C in the rubber state is about 7.1 MPa. The decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 3 at a mass loss of 5% was 524 ° C, and the residue at 800 ° C was 54.5%. The high temperature resistant thermoplastic shape memory polyimide prepared in Example 3 was folded 180° on a hot plate at 310 ° C to return to the original shape for 31 s.
实施例4：一种耐高温热塑性形状记忆聚酰亚胺的制备方法，是按以下步骤完成的：Example 4: A method for preparing a high temperature resistant thermoplastic shape memory polyimide was carried out by the following steps:
一、溶解4,4'-二氨基二苯醚单体：将1.7mmol 4,4'-二氨基二苯醚单体加入到10mLN,N'-二甲基乙酰胺中，在室温和干燥的氮气气氛下搅拌至4,4'-二氨基二苯醚单体完全溶解，得到二胺溶液；1. Dissolving 4,4'-diaminodiphenyl ether monomer: Add 1.7 mmol of 4,4'-diaminodiphenyl ether monomer to 10 mL of N,N'-dimethylacetamide at room temperature and dry Stirring under nitrogen atmosphere until the 4,4'-diaminodiphenyl ether monomer is completely dissolved to obtain a diamine solution;
二、制备溶胶凝胶状聚酰胺酸：将1.7mmol 4,4'-(六氟异丙烯)二酞酸酐单体分5次加入到二胺溶液中，在室温条件下和搅拌速度为300r/min的条件下搅拌26h，得到溶胶凝胶状聚酰胺酸；2. Preparation of sol-gel polyamic acid: 1.7 mmol of 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 5 portions at room temperature and the stirring speed was 300 r / Stirring under the condition of min for 26 h to obtain a sol-gel polyamic acid;
三、去除残留气泡：将溶胶凝胶状聚酰胺酸在70℃的真空干燥箱中干燥处理2h，得到溶胶凝胶状不含气泡的聚酰胺酸；3. Removing residual bubbles: drying the sol-gel polyamic acid in a vacuum oven at 70 ° C for 2 h to obtain a sol-gel-like polystyrene containing no bubbles;
四、热酰亚胺化：将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min的升温速率从室温开始升温至70℃，并在温度为70℃保温2h；再以1℃/min的升温速率升温至130℃，并在温度为130℃下保温2h；再以1℃/min的升温速率升温至180℃，并在温度为180℃下保温2h；以2℃/min的升温速率至240℃，并在温度为240℃下保温1h；再以2℃/min的升温速率升温至280℃，并在温度为280℃下保温1h；再以2℃/min的升温速率升温至330℃，并在温度为330℃下保温1h；最后以2℃/min的降温速率从温度为330℃降温至室温，得到聚酰胺薄膜的基板。4, thermal imidization: the sol-gel-like polystyrene acid is poured onto the substrate, the temperature is raised from room temperature to 70 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 70 ° C for 2 h; Then, the temperature was raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 130 ° C for 2 h; then the temperature was raised to 180 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 180 ° C for 2 h; The heating rate of °C/min is up to 240 °C, and the temperature is kept at 240 °C for 1 h; then the temperature is raised to 280 °C at a heating rate of 2 °C/min, and the temperature is maintained at 280 °C for 1 h; then at 2 °C/min. The heating rate was raised to 330 ° C, and the temperature was maintained at 330 ° C for 1 h; finally, the temperature was lowered from 330 ° C to room temperature at a cooling rate of 2 ° C / min to obtain a substrate of a polyamide film.
五、脱膜：将聚酰胺薄膜的基板置于蒸馏水中，使聚酰胺薄膜从聚酰胺薄膜的基板上脱落，再使用蒸馏水将聚酰胺薄膜冲洗干净，最后在温度为180℃的条件下加热400min，得到耐高温热塑性形状记忆聚酰亚胺。5. Stripping: The substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 180 ° C for 400 min. A high temperature resistant thermoplastic shape memory polyimide is obtained.
使用凝胶渗透色谱仪测得实施例4制备的耐高温热塑性形状记忆聚酰亚胺的重均分子量为94.2kg/mol。The weight average molecular weight of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 4 was measured by gel permeation chromatography to be 94.2 kg/mol.
使用凝胶渗透色谱仪测得实施例4制备的耐高温热塑性形状记忆聚酰亚胺的结构式为： The structural formula of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 4 was measured using a gel permeation chromatograph:
Figure PCTCN2015070308-appb-000012
Figure PCTCN2015070308-appb-000012
实施例4制备的耐高温热塑性形状记忆聚酰亚胺的玻璃化转变温度Tg为315℃。常温即30℃下玻璃态时的存储模量为2176MPa；高温335℃即Tg+20℃时橡胶态时的存储模量约为7.8MPa。实施例4制备的耐高温热塑性形状记忆聚酰亚胺质量损失为5％时的分解温度为523℃，在800℃下的残留为56.5％。实施例4制备的耐高温热塑性形状记忆聚酰亚胺在310℃热台上折叠180°回复到原始形状历时38s。High Temperature Thermoplastic shape memory Preparation Example 4 polyimide has a glass transition temperature T g of 315 ℃. The storage modulus at room temperature, that is, the glass state at 30 ° C is 2176 MPa; the storage modulus at the high temperature of 335 ° C, that is, T g + 20 ° C in the rubber state is about 7.8 MPa. The decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 4 at a mass loss of 5% was 523 ° C, and the residue at 800 ° C was 56.5%. The high temperature resistant thermoplastic shape memory polyimide prepared in Example 4 was folded 180° on a hot plate at 310 ° C to return to the original shape for 38 s.
实施例5：一种耐高温热塑性形状记忆聚酰亚胺的制备方法，是按以下步骤完成的：Example 5: A method for preparing a high temperature resistant thermoplastic shape memory polyimide was carried out by the following steps:
一、溶解4,4'-二氨基二苯醚单体：将2.0mmol 4,4'-二氨基二苯醚单体加入到10mLN,N'-二甲基乙酰胺中，在室温和干燥的氮气气氛下搅拌至4,4'-二氨基二苯醚单体完全溶解，得到二胺溶液；1. Dissolving 4,4'-diaminodiphenyl ether monomer: 2.0 mmol of 4,4'-diaminodiphenyl ether monomer was added to 10 mL of N,N'-dimethylacetamide at room temperature and dried. Stirring under nitrogen atmosphere until the 4,4'-diaminodiphenyl ether monomer is completely dissolved to obtain a diamine solution;
二、制备溶胶凝胶状聚酰胺酸：将2.0mmol 4,4'-(六氟异丙烯)二酞酸酐单体分5次加入到二胺溶液中，在室温条件下和搅拌速度为400r/min的条件下搅拌28h，得到溶胶凝胶状聚酰胺酸；2. Preparation of sol-gel polyamic acid: 2.0 mmol of 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 5 portions at room temperature and the stirring speed was 400 r/ Stirring under the condition of min for 28 h to obtain a sol-gel polyamic acid;
三、去除残留气泡：将溶胶凝胶状聚酰胺酸在80℃的真空干燥箱中干燥处理1.5h，得到溶胶凝胶状不含气泡的聚酰胺酸；3. Removing residual bubbles: drying the sol-gel polyamic acid in a vacuum oven at 80 ° C for 1.5 h to obtain a sol-gel-like polystyrene containing no bubbles;
四、热酰亚胺化：将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以2℃/min的升温速率从室温开始升温至90℃，并在温度为90℃保温2h；再以2℃/min的升温速率升温至140℃，并在温度为140℃下保温2h；再以2℃/min的升温速率升温至190℃，并在温度为190℃下保温2h；以2℃/min的升温速率至250℃，并在温度为250℃下保温2h；再以2℃/min的升温速率升温至290℃，并在温度为290℃下保温2h；再以2℃/min的升温速率升温至340℃，并在温度为340℃下保温2h；最后以2℃/min的降温速率从温度为340℃降温至室温，得到聚酰胺薄膜的基板。4. Thermal imidization: the sol-gel-like polystyrene acid without bubbles is poured onto the substrate, and the temperature is raised from room temperature to 90 ° C at a heating rate of 2 ° C / min, and the temperature is maintained at 90 ° C for 2 h; Then, the temperature was raised to 140 ° C at a heating rate of 2 ° C / min, and the temperature was maintained at 140 ° C for 2 h; then the temperature was raised to 190 ° C at a heating rate of 2 ° C / min, and the temperature was maintained at 190 ° C for 2 h; The heating rate of °C/min is up to 250 °C, and the temperature is kept at 250 °C for 2 h; then the temperature is raised to 290 °C at a heating rate of 2 °C/min, and the temperature is maintained at 290 °C for 2 h; then at 2 °C/min. The heating rate was raised to 340 ° C, and the temperature was maintained at 340 ° C for 2 h; finally, the temperature was lowered from 340 ° C to room temperature at a cooling rate of 2 ° C / min to obtain a substrate of a polyamide film.
五、脱膜：将聚酰胺薄膜的基板置于蒸馏水中，使聚酰胺酸薄膜从聚酰胺薄膜的基板上脱落，再使用蒸馏水将聚酰胺薄膜冲洗干净，最后在温度为180℃的条件下加热360min，得到耐高温热塑性形状记忆聚酰亚胺。5. Stripping: The substrate of the polyamide film is placed in distilled water to remove the polyamic acid film from the substrate of the polyamide film, and then the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 180 ° C. At 360 min, a high temperature resistant thermoplastic shape memory polyimide was obtained.
使用凝胶渗透色谱仪测得实施例5制备的耐高温热塑性形状记忆聚酰亚胺的重均分子量为104.6kg/mol。The weight average molecular weight of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 5 was measured by gel permeation chromatography to be 104.6 kg/mol.
使用凝胶渗透色谱仪测得实施例5制备的耐高温热塑性形状记忆聚酰亚胺的结构式为： The structural formula of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 5 was measured using a gel permeation chromatograph:
Figure PCTCN2015070308-appb-000013
Figure PCTCN2015070308-appb-000013
实施例5制备的耐高温热塑性形状记忆聚酰亚胺的玻璃化转变温度Tg为319℃。常温即30℃下玻璃态时的存储模量为2568MPa；高温339℃即Tg+20℃时橡胶态时的存储模量约为8.7MPa。实施例5制备的耐高温热塑性形状记忆聚酰亚胺质量损失为5％时的分解温度为526℃，在800℃下的残留为57.6％。实施例5制备的耐高温热塑性形状记忆聚酰亚胺在310℃热台上折叠180°回复到原始形状历时35s。The high temperature resistant thermoplastic shape memory polyimide prepared in Example 5 had a glass transition temperature T g of 319 °C. The storage modulus at room temperature, that is, the glass state at 30 ° C is 2568 MPa; the storage modulus at the high temperature of 339 ° C, that is, T g + 20 ° C in the rubber state is about 8.7 MPa. The decomposition temperature at which the mass loss resistance of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 5 was 5% was 526 ° C, and the residue at 800 ° C was 57.6%. The high temperature resistant thermoplastic shape memory polyimide prepared in Example 5 was folded 180° on a hot plate at 310 ° C to return to the original shape for 35 s.
当然，本发明还可有其他多种实施例，在不背离本发明精神及其实质的情况下，熟悉本领域的技术人员可根据本发明做出各种相应的改变和变形，但这些相应的改变和变形都应属于本发明所附的权利要求的保护范围。 The invention may, of course, be embodied in various other embodiments and various modifications and changes can be made in accordance with the present invention without departing from the spirit and scope of the invention. Changes and modifications are intended to be included within the scope of the appended claims.

Claims (10)

  1. 一种耐高温热塑性形状记忆聚酰亚胺，其特征在于一种耐高温热塑性形状记忆聚酰亚胺由4,4'-(六氟异丙烯)二酞酸酐和4,4'-二氨基二苯醚作为反应单体制备而成；所述的4,4'-(六氟异丙烯)二酞酸酐单体与4,4'-二氨基二苯醚单体的物质的量比为1:1。A high temperature resistant thermoplastic shape memory polyimide characterized by a high temperature resistant thermoplastic shape memory polyimide comprising 4,4'-(hexafluoroisopropene) dicarboxylic anhydride and 4,4'-diamino The phenyl ether is prepared as a reactive monomer; the ratio of the amount of the 4,4′-(hexafluoroisopropene) diphthalic anhydride monomer to the 4,4′-diaminodiphenyl ether monomer is 1: 1.
  2. 根据权利要求1所述的一种耐高温热塑性形状记忆聚酰亚胺，其特征在于一种耐高温热塑性形状记忆聚酰亚胺的结构式为：A high temperature resistant thermoplastic shape memory polyimide according to claim 1, wherein the structural formula of a high temperature resistant thermoplastic shape memory polyimide is:
    Figure PCTCN2015070308-appb-100001
    Figure PCTCN2015070308-appb-100001
    其中，所述的n的范围为128～172。Wherein, the range of n is from 128 to 172.
  3. 根据权利要求2所述的一种耐高温热塑性形状记忆聚酰亚胺，其特征在于一种耐高温热塑性形状记忆聚酰亚胺的重均分子量为77.8kg/mol～104.6kg/mol。A high temperature resistant thermoplastic shape memory polyimide according to claim 2, wherein a high temperature resistant thermoplastic shape memory polyimide has a weight average molecular weight of from 77.8 kg/mol to 104.6 kg/mol.
  4. 根据权利要求2所述的一种耐高温热塑性形状记忆聚酰亚胺，其特征在于所述的n的范围为130～170。A high temperature resistant thermoplastic shape memory polyimide according to claim 2, wherein said n ranges from 130 to 170.
  5. 如权利要求1所述的一种耐高温热塑性形状记忆聚酰亚胺的制备方法，其特征在于一种耐高温热塑性形状记忆聚酰亚胺的制备方法是按以下步骤完成的：The method for preparing a high temperature resistant thermoplastic shape memory polyimide according to claim 1, wherein the preparation method of the high temperature resistant thermoplastic shape memory polyimide is completed by the following steps:
    一、溶解4,4'-二氨基二苯醚单体：将4,4'-二氨基二苯醚单体加入到N,N'-二甲基乙酰胺中，在室温和干燥的氮气气氛下搅拌至4,4'-二氨基二苯醚单体完全溶解，得到二胺溶液；1. Dissolving 4,4'-diaminodiphenyl ether monomer: adding 4,4'-diaminodiphenyl ether monomer to N,N'-dimethylacetamide at room temperature and a dry nitrogen atmosphere Stirring until the 4,4'-diaminodiphenyl ether monomer is completely dissolved to obtain a diamine solution;
    步骤一所述的4,4'-二氨基二苯醚单体的物质的量与N,N'-二甲基乙酰胺的体积比为(0.1mmol～0.2mmol):1mL；The volume ratio of the amount of the 4,4'-diaminodiphenyl ether monomer to the N,N'-dimethylacetamide in the first step is (0.1 mmol to 0.2 mmol): 1 mL;
    二、制备溶胶凝胶状聚酰胺酸：将4,4'-(六氟异丙烯)二酞酸酐单体分3次～6次加入到二胺溶液中，在室温和搅拌速度为300r/min～400/min的条件下搅拌25h～30h，得到溶胶凝胶状聚酰胺酸；2. Preparation of sol-gel polyamic acid: 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 3 to 6 times at room temperature and stirring speed was 300 r/min. Stirring for 25 to 30 hours under conditions of ~400/min to obtain a sol-gel polyamic acid;
    步骤二所述的4,4'-(六氟异丙烯)二酞酸酐单体与二胺溶液中4,4'-二氨基二苯醚单体的物质的量比为1:1；The ratio of the amount of the 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer to the 4,4'-diaminodiphenyl ether monomer in the diamine solution is 1:1;
    三、去除残留气泡：将溶胶凝胶状聚酰胺酸在50℃～80℃的真空干燥箱中干燥处理1.5h～2.5h，得到溶胶凝胶状不含气泡的聚酰胺酸；3. Removing residual bubbles: drying the sol-gel polyamic acid in a vacuum oven at 50 ° C to 80 ° C for 1.5 h to 2.5 h to obtain a sol-gel-like polyamic acid containing no bubbles;
    四、热酰亚胺化：将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min～2℃/min的升温速率从室温开始升温至60℃～90℃，并在温度为60℃～90℃下保温1h～2h；再以 1℃/min～2℃/min的升温速率升温至120℃～140℃，并在温度为120℃～140℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至170℃～190℃，并在温度为170℃～190℃下保温1h～2h；再以1℃/min～2℃/min的升温速率至220℃～250℃，并在温度为220℃～250℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至270℃～290℃，并在温度为270℃～290℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至320℃～340℃，并在温度为320℃～340℃下保温1h～2h；最后以1℃/min～2℃/min的降温速率从温度为320℃～340℃降温至室温，得到聚酰胺薄膜的基板；4. Thermal imidization: the sol-gel-like polystyrene acid is poured onto the substrate, and the temperature is raised from room temperature to 60 ° C to 90 ° C at a heating rate of 1 ° C / min to 2 ° C / min, and Keep at a temperature of 60 ° C ~ 90 ° C for 1 h ~ 2 h; The heating rate of 1 ° C / min ~ 2 ° C / min is raised to 120 ° C ~ 140 ° C, and the temperature is maintained at 120 ° C ~ 140 ° C for 1 h ~ 2 h; and then the temperature rise rate of 1 ° C / min ~ 2 ° C / min To 170 ° C ~ 190 ° C, and the temperature is maintained at 170 ° C ~ 190 ° C for 1 h ~ 2h; then at a temperature increase rate of 1 ° C / min ~ 2 ° C / min to 220 ° C ~ 250 ° C, and at a temperature of 220 ° C ~ Incubate at 250 ° C for 1 h ~ 2 h; then increase the temperature to 270 ° C ~ 290 ° C at a temperature increase rate of 1 ° C / min ~ 2 ° C / min, and heat at 270 ° C ~ 290 ° C for 1 h ~ 2 h; then 1 ° C / The temperature rise rate of min~2°C/min is raised to 320°C～340°C, and the temperature is kept at 320°C～340°C for 1h～2h; finally, the temperature is from 320°C to 2°C/min. Decreasing to room temperature from ° C to 340 ° C to obtain a substrate of a polyamide film;
    五、脱膜：将聚酰胺薄膜的基板置于蒸馏水中，使聚酰胺薄膜从聚酰胺薄膜的基板上脱落，再使用蒸馏水将聚酰胺薄膜冲洗干净，最后在温度为120℃～180℃的条件下加热360min～600min，得到耐高温热塑性形状记忆聚酰亚胺。5. Stripping: The substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally at a temperature of 120 ° C to 180 ° C. The lower temperature is heated for 360 min to 600 min to obtain a high temperature resistant thermoplastic shape memory polyimide.
  6. 根据权利要求5所述的一种耐高温热塑性形状记忆聚酰亚胺的制备方法，其特征在于步骤一所述的4,4'-二氨基二苯醚单体的物质的量与N,N'-二甲基乙酰胺溶剂的体积比为(0.11mmol～0.19mmol):1mL。The method for preparing a high temperature resistant thermoplastic shape memory polyimide according to claim 5, wherein the amount of the 4,4'-diaminodiphenyl ether monomer in the first step is N, N The volume ratio of the '-dimethylacetamide solvent was (0.11 mmol to 0.19 mmol): 1 mL.
  7. 根据权利要求5所述的一种耐高温热塑性形状记忆聚酰亚胺的制备方法，其特征在于步骤三中将溶胶凝胶状聚酰胺酸在55℃～75℃的真空干燥箱中干燥处理1.5h～2h，得到溶胶凝胶状不含气泡的聚酰胺酸。The method for preparing a high temperature resistant thermoplastic shape memory polyimide according to claim 5, characterized in that in the third step, the sol-gel polyamic acid is dried in a vacuum drying oven at 55 ° C to 75 ° C. From h to 2 h, a sol-gel-like polyamic acid containing no bubbles was obtained.
  8. 根据权利要求5所述的一种耐高温热塑性形状记忆聚酰亚胺的制备方法，其特征在于步骤四中将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min～2℃/min的升温速率从室温开始升温至70℃～80℃，并在温度为70℃～80℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至130℃～140℃，并在温度为130℃～140℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至170℃～190℃，并在温度为170℃～190℃下保温1h～2h；再以1℃/min～2℃/min的升温速率至220℃～250℃，并在温度为220℃～250℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至270℃～290℃，并在温度为270℃～290℃下保温1h～2h；再以1℃/min～2℃/min的升温速率升温至320℃～330℃，并在温度为320℃～330℃下保温1h～2h；最后以1℃/min～2℃/min的降温速率从温度为320℃～330℃降温至室温，得到聚酰胺薄膜的基板。The method for preparing a high temperature resistant thermoplastic shape memory polyimide according to claim 5, wherein in the fourth step, the sol-gel-like polystyrene-free polyamic acid is poured onto the substrate to form a sol-gel. The bubble-free polyamic acid is poured onto the substrate, and the temperature is raised from room temperature to 70 ° C to 80 ° C at a heating rate of 1 ° C / min to 2 ° C / min, and is kept at a temperature of 70 ° C to 80 ° C for 1 h to 2 h. Then, the temperature is raised to 130 ° C ~ 140 ° C at a heating rate of 1 ° C / min ~ 2 ° C / min, and the temperature is maintained at 130 ° C ~ 140 ° C for 1 h ~ 2 h; and then 1 ° C / min ~ 2 ° C / min The heating rate is raised to 170 ° C ~ 190 ° C, and the temperature is maintained at 170 ° C ~ 190 ° C for 1 h ~ 2 h; then at a temperature increase rate of 1 ° C / min ~ 2 ° C / min to 220 ° C ~ 250 ° C, and at the temperature Incubate at 220 ° C ~ 250 ° C for 1 h ~ 2 h; then increase the temperature to 270 ° C ~ 290 ° C at a temperature increase rate of 1 ° C / min ~ 2 ° C / min, and heat at 270 ° C ~ 290 ° C for 1 h ~ 2 h; The heating rate of 1 ° C / min ~ 2 ° C / min is raised to 320 ° C ~ 330 ° C, and the temperature is maintained at 320 ° C ~ 330 ° C for 1 h ~ 2 h; finally from 1 ° C / min ~ 2 ° C / min cooling rate from Temperature is The substrate was cooled to room temperature at 320 ° C to 330 ° C to obtain a substrate of a polyamide film.
  9. 根据权利要求5所述的一种耐高温热塑性形状记忆聚酰亚胺的制备方法，其特征在于步骤四中将溶胶凝胶状不含气泡的聚酰胺酸倒入基板上，以1℃/min的升温速率从室温开始升温至60℃，并在温度为60℃下保温2h；再以1℃/min的升温速率升温至120℃，并在温度为120℃下保温1h；再以1℃/min的升温速率升温至170℃，并在温度为170℃下保 温1h；再以1℃/min的升温速率至220℃，并在温度为220℃下保温1h；再以1℃/min的升温速率升温至270℃，并在温度为270℃下保温1h；再以1℃/min的升温速率升温至330℃，并在温度为330℃下保温1h；最后以1℃/min的降温速率从温度为330℃降温至室温，得到聚酰胺薄膜的基板。The method for preparing a high temperature resistant thermoplastic shape memory polyimide according to claim 5, characterized in that in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto the substrate at 1 ° C/min. The heating rate is raised from room temperature to 60 ° C, and the temperature is maintained at 60 ° C for 2 h; then the temperature is raised to 120 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 120 ° C for 1 h; and then 1 ° C / The heating rate of min is raised to 170 ° C and maintained at a temperature of 170 ° C. 1 h; further at a temperature increase rate of 1 ° C / min to 220 ° C, and at a temperature of 220 ° C for 1 h; then at a temperature increase rate of 1 ° C / min to 270 ° C, and incubated at a temperature of 270 ° C for 1 h; The temperature was raised to 330 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 330 ° C for 1 h; finally, the temperature was lowered from 330 ° C to room temperature at a cooling rate of 1 ° C / min to obtain a substrate of a polyamide film.
  10. 根据权利要求5所述的一种耐高温热塑性形状记忆聚酰亚胺的制备方法，其特征在于步骤五中将聚酰胺薄膜的基板置于蒸馏水中，使聚酰胺薄膜从聚酰胺薄膜的基板上脱落，再使用蒸馏水将聚酰胺薄膜冲洗干净，最后在温度为130℃～170℃的条件下加热450min～550min，得到耐高温热塑性形状记忆聚酰亚胺。 The method for preparing a high temperature resistant thermoplastic shape memory polyimide according to claim 5, wherein in step 5, the substrate of the polyamide film is placed in distilled water to make the polyamide film from the substrate of the polyamide film. After falling off, the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 130 ° C to 170 ° C for 450 min to 550 min to obtain a high temperature resistant thermoplastic shape memory polyimide.
PCT/CN2015/070308 2014-05-23 2015-01-08 High temperature-resistant thermoplastic shape-memory polyimide and preparation method therefor WO2015176545A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410221970.4A CN103980492B (en) 2014-05-23 2014-05-23 A kind of preparation method of high-temperature-resistant thermoplastic shape memory polyimides
CN201410221970.4 2014-05-23

Publications (1)

Publication Number Publication Date
WO2015176545A1 true WO2015176545A1 (en) 2015-11-26

Family

ID=51272676

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/070308 WO2015176545A1 (en) 2014-05-23 2015-01-08 High temperature-resistant thermoplastic shape-memory polyimide and preparation method therefor

Country Status (2)

Country Link
CN (1) CN103980492B (en)
WO (1) WO2015176545A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103980492B (en) * 2014-05-23 2016-06-29 哈尔滨工业大学 A kind of preparation method of high-temperature-resistant thermoplastic shape memory polyimides
CN105254888B (en) * 2015-11-23 2019-01-22 厦门理工学院 Polyimides ionomer and preparation method thereof
CN105542460B (en) * 2016-03-01 2018-03-27 哈尔滨工业大学 A kind of high temperature polyimide heat-shrink tube and preparation method thereof
CN105778092B (en) * 2016-03-09 2018-03-16 哈尔滨工业大学 A kind of PEI high temperature heat-shrink tube and preparation method thereof
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
CN110894294B (en) * 2019-12-09 2021-01-08 中国科学院长春应用化学研究所 High-temperature-resistant fluorine-containing polyimide heat-shrinkable tube and preparation method thereof
CN113417145B (en) * 2021-05-17 2022-03-15 东华大学 Bidirectional shape memory polyimide fiber cloth and preparation method thereof
CN114045028A (en) * 2021-12-10 2022-02-15 东华大学 Deformable thermoplastic composite material and preparation method thereof
CN114773601B (en) * 2022-05-24 2023-08-22 哈尔滨工业大学 High Tg and high modulus shape memory flame-retardant polyimide, and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003022955A1 (en) * 2001-09-11 2003-03-20 Nessdisplay Co., Ltd. Organic electroluminescent device having a polyimide hole transport layer
CN101089030A (en) * 2007-06-18 2007-12-19 南京工业大学 Prepn process of polyimide microsphere
CN103467985A (en) * 2013-09-22 2013-12-25 株洲时代电气绝缘有限责任公司 Polyimide thin film
CN103980492A (en) * 2014-05-23 2014-08-13 哈尔滨工业大学 High-temperature-resistant thermoplastic shape memory polyimide and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5502156A (en) * 1994-07-28 1996-03-26 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Electrically conducting polyimide film containing tin complexes
KR101225842B1 (en) * 2007-08-27 2013-01-23 코오롱인더스트리 주식회사 Colorless polyimide film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003022955A1 (en) * 2001-09-11 2003-03-20 Nessdisplay Co., Ltd. Organic electroluminescent device having a polyimide hole transport layer
CN101089030A (en) * 2007-06-18 2007-12-19 南京工业大学 Prepn process of polyimide microsphere
CN103467985A (en) * 2013-09-22 2013-12-25 株洲时代电气绝缘有限责任公司 Polyimide thin film
CN103980492A (en) * 2014-05-23 2014-08-13 哈尔滨工业大学 High-temperature-resistant thermoplastic shape memory polyimide and preparation method thereof

Also Published As

Publication number Publication date
CN103980492A (en) 2014-08-13
CN103980492B (en) 2016-06-29

Similar Documents

Publication Publication Date Title
WO2015176545A1 (en) High temperature-resistant thermoplastic shape-memory polyimide and preparation method therefor
KR101922791B1 (en) A quick responsive, shape memory thermoset polyimide and preparation method thereof
CN108641082B (en) Thermosetting polyimide prepolymer and preparation method and application thereof
CN105461922B (en) A kind of low viscosity thermoset polyimide resin and its preparation method and application
CN106928481A (en) The optimization preparation method of Kapton
CN102604091B (en) Polyimide containing benzimidazole unit and preparation method thereof
CN102352039B (en) Soluble functional polyimide based on fluorene structure as well as preparation method and application thereof
CN103788651B (en) Polyamic acid solution of low apparent viscosity and preparation method thereof
CN108456309B (en) High-performance thermosetting shape memory polyimide capable of being laminated and welded
CN102757560A (en) Soluble functional polyimide with carbazole structure and preparation method and application thereof
CN103980490A (en) Shape memory polyimide prepared by virtue of chemical imidization and preparation method thereof
CN103289402A (en) Novel transparent polyimide film, pre-polymer thereof, and preparation method thereof
CN107602857A (en) The preparation method and application of polyimides
CN111019129A (en) Low-thermal expansion coefficient soluble polyimide resin powder and preparation method thereof
CN103992478B (en) Heat safe solvable fusible polyimide resin and preparation method thereof
CN104017213A (en) Shape memory polyether imide with high glass-transition temperature and preparation method thereof
CN104530429A (en) High-fluidity wide-processing-widow polyimide pre-polymer and preparation method thereof
CN105239196B (en) A kind of preparation method of polyamidoimide fibrid
CN111303004B (en) Imide monomer as amino end cap, organic hybridization film and preparation method thereof
CN101602856A (en) Polyimide resin of a kind of terminated with phenylacetylene anhydride naphthalene groups and preparation method thereof and purposes
CN104974362B (en) A kind of preparation process of Kapton
CN112961347B (en) Low-viscosity high-temperature-resistant thermosetting polyimide resin and preparation method and application thereof
CN113717384A (en) Modified polyamide-imide material and preparation method thereof
CN103086911A (en) Oligomer, polyimide film/fiber containing oligomer and preparation method of polyimide film/fiber containing oligomer
CN107602856B (en) Thermosetting polyimide prepolymer with high solubility, preparation method and application thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15795581

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15795581

Country of ref document: EP

Kind code of ref document: A1