WO2019165581A1 - 一种超疏水电热环氧树脂复合材料及其制备与自修复方法 - Google Patents

一种超疏水电热环氧树脂复合材料及其制备与自修复方法 Download PDF

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WO2019165581A1
WO2019165581A1 PCT/CN2018/077460 CN2018077460W WO2019165581A1 WO 2019165581 A1 WO2019165581 A1 WO 2019165581A1 CN 2018077460 W CN2018077460 W CN 2018077460W WO 2019165581 A1 WO2019165581 A1 WO 2019165581A1
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epoxy resin
electrothermal
composite material
parts
resin composite
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PCT/CN2018/077460
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English (en)
French (fr)
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梁国正
张又豪
顾嫒娟
袁莉
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苏州大学张家港工业技术研究院
苏州大学
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Priority to PCT/CN2018/077460 priority Critical patent/WO2019165581A1/zh
Publication of WO2019165581A1 publication Critical patent/WO2019165581A1/zh
Priority to US17/003,569 priority patent/US11739067B2/en

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D327/00Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4064Curing agents not provided for by the groups C08G59/42 - C08G59/66 sulfur containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/042Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/0427Coating with only one layer of a composition containing a polymer binder
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the present invention relates to a superhydrophobic electrothermal epoxy resin composite material, and a preparation and self-repairing method thereof.
  • the lower r g ensures that they are self-repairing at a certain temperature (RT ⁇ 200 ° C) and time (0 ⁇ 24 h), their poor heat resistance can not meet the requirements of the resin for wind power blades. , can not withstand the high temperature generated by the electric heating coating deicing.
  • the polymer-based reversible self-repairing electrothermal coating which has been reported so far also has a problem of poor heat resistance (r g is about -120 to 20 ° C).
  • r g is about -120 to 20 ° C.
  • the rubbery coating under the influence of its own gravity has the potential to undergo large deformations.
  • self-healing superhydrophobic coatings mainly rely on migration rearrangement of low surface energy substances (long-chain aliphatic hydrocarbons, polyfluoro compounds or polysiloxanes) or controlled release of low surface energy substances by microcapsules.
  • Both of these repair methods are based on the premise that the micro-nano structure on the surface of the super-hydrophobic coating remains unchanged before and after repair. Only self-repair for slight friction or oxidation can be achieved, and major damage such as cracking or peeling of the resin and the coating can be achieved. Powerless.
  • Multi-layer composite materials used to repair the cracking and interlaminar peeling of wind turbine blades and to ensure their anti-icing and deicing effect is a topic of great application value.
  • a method for preparing a superhydrophobic electrothermal epoxy resin composite material comprising the following steps:
  • the present invention also discloses a method for preparing an electrothermal epoxy resin composite material, comprising the following steps:
  • the preparation method of the 2,2'-dithioglycolic anhydride is as follows:
  • the ester solvent and the ester solvent are independently selected from one or more of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, and ethyl propionate.
  • the perfluorocarboxylic acid is one or more of perfluorooctanoic acid, perfluorodecanoic acid, and perfluorodecanoic acid.
  • the epoxy resin is a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, an aliphatic epoxy compound, an alicyclic epoxy compound One of them, or any combination thereof;
  • the carbon nanotube is one of unsurfaced single-walled carbon nanotubes, multi-walled carbon nanotubes, or any combination thereof.
  • the acid anhydride is one of acetic anhydride, trifluoroacetic anhydride, or any combination thereof.
  • the present invention discloses a superhydrophobic electrothermal epoxy resin composite material prepared by the above method for preparing a superhydrophobic electrothermal epoxy resin composite material; or an electrothermal epoxy resin composite material prepared by the above method for preparing an electrothermal epoxy resin composite material.
  • the invention also discloses the use of 2,2'-dithioglycolic anhydride in the preparation of the above superhydrophobic electrothermal epoxy resin composite material or the above electrothermal epoxy resin composite material.
  • the present invention further discloses a self-repairing method for the above superhydrophobic electrothermal epoxy resin composite material, comprising the steps of: fixing the cross section of the damaged superhydrophobic electrothermal epoxy resin composite material with a clamp and closely fitting, at a temperature of The self-repair of the superhydrophobic electrothermal epoxy resin composite material is completed under the condition of 160 to 200 ° C for 1 to 3 hours.
  • the present invention further discloses a self-repairing method of the above-mentioned electrothermal epoxy resin composite material, comprising the following steps, fixing the cross section of the damaged electrothermal epoxy resin composite material with a clamp and closely fitting it at a temperature of 160 to 200°; The treatment under C conditions for 1 to 3 hours completes the self-repair of the electrothermal epoxy resin composite.
  • the superhydrophobic electrothermal epoxy resin composite material provided by the invention utilizes the exchange reaction of the reversible disulfide bond in the resin layer to drive the superhydrophobic layer to repair from bottom to top, thereby effectively repairing major damage such as cracking and peeling and still after repairing Has a good super hydrophobic effect.
  • the superhydrophobic electrothermal epoxy resin composite material provided by the invention has the additional reversible self-repairing performance while satisfying the requirements of the wind and ice deicing technology of the wind power blade, and can effectively ensure the operation safety of the wind turbine and prolong the service life.
  • Example 1 is a schematic diagram showing the synthesis scheme of 2,2'-dithioglycolic anhydride provided in Example 1 (reaction formula).
  • FIG. 2 is a nuclear magnetic resonance spectrum (OH-NMR) of the product prepared in Example 1.
  • Example 3 is an infrared spectrum of a reversible self-repairing epoxy resin and an electrothermal epoxy resin composite prepared in Example 1.
  • Example 4 is a dynamic mechanical curve of a reversible self-repairing epoxy resin and an electrothermal epoxy resin composite material of Example 1.
  • Example 5 is a digital photograph of a static contact angle test of the electrothermal epoxy resin composite prepared in Example 1.
  • Example 6 is an infrared spectrum of the modified superhydrophobic copper powder prepared in Example 1.
  • Example 7 is an X-ray diffraction spectrum of the modified superhydrophobic copper powder prepared in Example 1.
  • FIG. 8 is a digital photograph of a static contact angle test of the superhydrophobic electrothermal epoxy resin composite prepared in Example 1.
  • Example 9 is a digital photo of electrothermal near-infrared imaging of the superhydrophobic electrothermal epoxy resin composite prepared in Example 1.
  • FIG. 10 is a digital photograph of electrothermal deicing of the superhydrophobic electrothermal epoxy resin composite prepared in Example 1.
  • FIG. 11 is a digital photograph of the self-healing effect of the superhydrophobic electrothermal epoxy resin composite prepared in Example 9.
  • Example 12 is a photograph of a static contact angle of the superhydrophobic electrothermal epoxy resin composite of Example 9 after self-healing.
  • 2,2'-dithioglycolic anhydride, 4.3 g of methylhexahydrophthalic anhydride and 0.05 g of 2-ethyl-4-methylimidazole are uniformly mixed to obtain prepolymer B; to prepolymer B Ethyl acetate and 2.07 g of non-surface-treated multi-walled carbon nanotubes were added, uniformly mixed, coated on the reversible self-repairing epoxy resin obtained in the step (2), and ethyl acetate was volatilized, followed by 80.
  • FIG. 1 it is a schematic diagram showing the synthesis scheme of 2,2'-dithioglycolic anhydride provided in Example 1 of the present invention (reaction formula).
  • the first step is an oxidation reaction of a thiol bond to form a disulfide bond having reversible characteristics;
  • the second step is a dehydration condensation reaction of a carboxyl group to form an acid anhydride which can be used for a curing reaction with an epoxy group.
  • FIG. 2 it is a nuclear magnetic resonance spectrum (-NMR) of 2,2'-dithioethanedioic acid and 2,2'-dithioglycolic anhydride prepared in Example 1 of the present invention.
  • -NMR nuclear magnetic resonance spectrum
  • FIG. 3 it is an infrared spectrum of a reversible self-repairing epoxy resin and an electrothermal epoxy resin composite prepared in Example 1 of the present invention.
  • the absorption peak at the point is the characteristic peak of CS in 2, 2'-dithioglycolic anhydride, indicating that 2,2'-dithioethanedianhydride has been melted.
  • CS characteristic peak of 2, 2'-dithioglycolic anhydride
  • FIG. 4 it is a dynamic mechanical curve of a reversible self-repairing epoxy resin and an electrothermal epoxy resin composite prepared in Example 1 of the present invention.
  • the peak top temperature of the dielectric loss tangent (tan6) is a single tan6 peak of the 7> reversible self-repairing epoxy resin of resin and composite material, and its g is about 113 °C.
  • the dynamic mechanical curve of the electrothermal epoxy resin composite showed a shoulder peak around 100 °C. Obviously, the appearance of the shoulder is caused by the entanglement of the epoxy polymer chain on the surface of the carbon nanotube to form a resin/filler overlayer.
  • the peak height of tan6 of the electrothermal epoxy resin composite is lower than that of the reversible self-repairing epoxy resin, which indicates that the carbon nanotubes have an inhibitory effect on molecular chain motion.
  • the vast majority of reversible self-repairing electrothermal composites reported in the past are hydrogels and elastomers, g is generally lower than 20 ° C, the main application areas are sensors and wearable devices.
  • the 7% of the electrothermal epoxy resin composite prepared by the present invention was 113 °C.
  • the higher r g can make the electrothermal epoxy composite material have better heat resistance, and it is enough to withstand the Joule heat generated by the material after energization, which is of great significance for maintaining the three-dimensional size of the wind power blade.
  • FIG. 5 it is a digital photograph of the static contact angle test of the electrothermal epoxy resin composite prepared in Example 1 of the present invention. As shown in Fig. 5a, the water droplets are scattered in the hemispherical shape on the surface of the electrothermal epoxy composite, and the corresponding static contact angle is 89.5. .
  • FIG. 6 it is an infrared spectrum of the modified superhydrophobic copper powder prepared in Example 1 of the present invention.
  • 16 60cm - and at 1464 to 1413cm 1-- band 1 respectively asymmetric perfluorodecanoic acid carboxylate stretching vibration and symmetric stretching vibration peak; and 1360cm - 1 and 1317cm - 1 belongs to the band at The stretching vibration peak of CF 3 in perfluorodecanoic acid, the band at 1198 cm -1 and 1140 cm -1 is the CF ⁇ stretching vibration peak in perfluorodecanoic acid.
  • This result indicates that the copper powder has been modified to have been encapsulated by CF 2 mc F 3 groups and has a lower surface energy.
  • FIG 7 it is an X-ray diffraction spectrum of the modified superhydrophobic copper powder prepared in Example 1 of the present invention. Of which, 29.48. , 36.34. , 42.39. And 61.43. The diffraction peak at the point is the characteristic peak of Cu 2 0, and 43.28.
  • the diffraction peak at the point is a characteristic peak of Cu.
  • the source of 0 may be the reaction of some Cu with oxygen.
  • FIG. 8 it is a digital photograph of the static contact angle test of the superhydrophobic electrothermal epoxy resin composite prepared in Example 1 of the present invention.
  • the surface of the electrothermal epoxy resin composite material is uniformly adhered to a layer of modified superhydrophobic copper
  • the water droplets on the surface of the obtained superhydrophobic electrothermal epoxy resin composite material are transformed into a nearly spherical shape (Fig. 8a), and the static contact angle of the surface is increased to 154.0. (Fig. 8b).
  • FIG. 8c A video screenshot of the surface slip angle test of the superhydrophobic electrothermal epoxy composite is shown in Figure 8c, when the composite has a sliding angle of about 3. At this time, water droplets can quickly roll off the surface of the material.
  • the above results show that the superhydrophobic electrothermal epoxy resin composite has good superhydrophobic properties similar to lotus leaves.
  • FIG. 9 it is a digital photograph of electrothermal near-infrared imaging of a superhydrophobic electrothermal epoxy resin composite prepared in Example 1 of the present invention.
  • the heating temperature of the composite can be effectively regulated by adjusting the voltage. According to Joule's law, the heating temperature of the superhydrophobic electrothermal epoxy resin composite increases with the increase of voltage.
  • the applied voltage is 15V
  • the maximum temperature of the composite material is stable at 96.7 ° C, which is lower than the g (113 ° C) of the reversible self-repairing epoxy resin and the electrothermal epoxy resin composite.
  • the good heat resistance of the composite material is effective. It is guaranteed to be stable in size and safe to use when heated and de-iced.
  • FIG 10 it is a digital photo of electrothermal deicing of a superhydrophobic electrothermal epoxy resin composite prepared in Example 1 of the present invention.
  • the composite is approximately 3 in the horizontal direction. Place, apply 10V voltage preheating at both ends, and then place a small amount of crushed ice on the surface. After 26 seconds, the crushed ice can be completely dissolved and automatically slipped from the surface of the composite without any droplets remaining. This phenomenon fully proves that the composite material has a good deicing effect under the joint action of the superhydrophobic surface and the electrothermal intermediate layer, and can be used as a wind and ice blade in the field of deicing and anti-icing.
  • 2,2'-dithioglycolic anhydride 15 g of methylhexahydrophthalic anhydride and 0.5 g of 2-ethyl-4-methylimidazole are uniformly mixed, and then according to 80 ° C / 2 h + 100 ° C / 2 h Curing at +120°C/2h+140°C/2h+160°C/4h, After natural cooling, the mold was released to obtain a reversible self-repairing epoxy resin.
  • 2,2'-dithioglycolic anhydride 1.5 g of methylhexahydrophthalic anhydride and 0.05 g of 2-ethyl-4-methylimidazole are uniformly mixed to obtain prepolymer B; to prepolymer B Methyl acetate and 1.06 g of untreated single-walled carbon nanotubes were added, uniformly mixed, coated on the reversible self-repairing epoxy resin prepared in the step (2), and volatilized with methyl acetate at 80 ° C / Curing is carried out in a process of 2h+100°C/2h+120°C/2h+140°C/2h+160°C/4h. After natural cooling, an electrothermal epoxy resin composite material is obtained, and r g exceeds iio°c.
  • the composite material is approximately 3 in the horizontal direction. Place, apply 10V voltage preheating at both ends, and then place a small amount of crushed ice on the surface. After 26 seconds, the crushed ice can be completely dissolved and automatically slipped from the surface of the composite without any droplets remaining. This phenomenon fully proves that the composite material has a good deicing effect under the joint action of the superhydrophobic surface and the electrothermal intermediate layer, and can be used as a field for deicing and anti-icing of wind power blades.
  • the fracture surface of the fractured superhydrophobic electrothermal epoxy resin composite material is fixed by a clamp and closely adhered, and treated at a temperature of 180 ° C for 2 hours, and the fractured samples can be rejoined together to complete self-repair and composite materials. It still retains its good superhydrophobic properties after self-healing.
  • 2-ethyl-4-methylimidazole is uniformly mixed, and then cured according to the process of 80 ° C / 2 h + 100 ° C / 2 h + 120 ° C / 2 h + 140 ° C / 2 h + 16 0 ° C / 4 h, After natural cooling, the mold was released to obtain a reversible self-repairing epoxy resin.
  • prepolymer C 2 -ethyl- 4 -methylimidazole is uniformly mixed to obtain prepolymer C; prepolymer C is coated on electrothermal epoxy resin composite material obtained in step (3), and modified superhydrophobic copper powder is further applied. It is uniformly dispersed on the prepolymer C, and then cured according to the process of 80 ° C / 2 h + 100 ° C / 2 h + 120 ° C / 2 h + 140 ° C / 2 h + 160 ° C / 4 h, after natural cooling, A superhydrophobic electrothermal epoxy resin composite material, the water droplets are scattered in the hemispherical shape on the surface of the electrothermal epoxy resin composite material, indicating that the superhydrophobic electrothermal epoxy resin composite material has a good similarity to the lotus leaf Super hydrophobic performance.
  • the composite material is approximately 3 in the horizontal direction. Place, apply 10V voltage preheating at both ends, and then place a small amount of crushed ice on the surface. After 27 seconds, the crushed ice can be completely dissolved and automatically slipped from the surface of the composite without any droplets remaining. This phenomenon fully proves that the composite material has a good deicing effect under the joint action of the superhydrophobic surface and the electrothermal intermediate layer, and can be used as a field for deicing and anti-icing of wind power blades.
  • the fracture surface of the fractured superhydrophobic electrothermal epoxy resin composite material is fixed by a clamp and closely adhered, and treated at a temperature of 200 ° C for 3 hours, and the fractured samples can be rejoined together to complete self-repair and composite materials. It still retains its good superhydrophobic properties after self-healing.
  • the specific steps are as follows: 120 g of 2-mercaptoacetic acid, 500 g of methyl propionate and 1.2 g of potassium iodide are uniformly mixed to form a solution A by mass, and the solution is slowly added to the solution A at a temperature of 25 ° C. After 85 g of 30 wt% hydrogen peroxide, the reaction was incubated for 2.5 h. After the reaction was completed, the solution was washed with 300 mL of saturated sodium sulfite solution, and methyl propionate was distilled off under reduced pressure to obtain 2,2'-dithioglycolic acid. .
  • 2,2'-dithioglycolic anhydride, 41 g of methylhexahydrophthalic anhydride and 0.5 g of 2-ethyl-4-methylimidazole are uniformly mixed, and then according to 80 ° C / 2 h + 100 ° C / 2 h
  • the process was carried out at +120 ° C / 2 h + 140 ° C / 2 h + 160 ° C / 4 h, and after natural cooling, the mold was released to obtain a reversible self-repairing epoxy resin.
  • 2,2'-dithioglycolic anhydride 4.1 g of methylhexahydrophthalic anhydride and 0.05 g of 2-ethyl-4-methylimidazole are uniformly mixed to obtain prepolymer B; to prepolymer B Ethyl propionate and 2.01 g of non-surface-treated multi-walled carbon nanotubes were added, uniformly mixed, coated on the reversible self-repairing epoxy resin obtained in the step (2), and volatilized with ethyl propionate according to 80.
  • 2,2'-dithioglycolic anhydride, 4.1 g of methylhexahydrophthalic anhydride and 0.05 g of 2-ethyl-4-methylimidazole are uniformly mixed to obtain a prepolymer C;
  • the modified superhydrophobic copper powder is uniformly dispersed on the prepolymer C, and then according to 80 ° C / 2 h + 100 ° C / 2 h + 12 0 Curing at °C/2h+140°C/2h+160°C/4h, after natural cooling, a superhydrophobic electrothermal epoxy resin composite material is obtained, and water droplets are scattered on the surface of the electrothermal epoxy resin composite material.
  • the hemispherical shape indicates that the superhydrophobic electrothermal epoxy resin composite has a good superhydrophobic property similar to that of a lotus leaf.
  • the composite material is approximately 3 in the horizontal direction. Place, apply 10V voltage preheating at both ends, and then place a small amount of crushed ice on the surface. After 26 seconds, the crushed ice can be completely dissolved and automatically slipped from the surface of the composite without any droplets remaining. This phenomenon fully proves that the composite material has a good deicing effect under the joint action of the superhydrophobic surface and the electrothermal intermediate layer, and can be used as a field for deicing and anti-icing of wind power blades.
  • the fracture surface of the fractured superhydrophobic electrothermal epoxy resin composite material is fixed by a clamp and closely adhered, and treated at a temperature of 160 ° C for 2 h, the fractured samples can be rejoined together to complete self-repair and composite materials. It still retains its good superhydrophobic properties after self-healing.
  • 2,2'-dithioglycolic anhydride, 3.4 g of methylhexahydrophthalic anhydride and 0.05 g of 2-ethyl-4-methylimidazole are uniformly mixed to obtain prepolymer B; to prepolymer B Ethyl acetate and methyl acetate and 1.09 g of untreated single-walled carbon nanotubes were added, uniformly mixed, and coated on the reversible self-repairing epoxy resin obtained in the step (2).
  • 2,2'-dithioglycolic anhydride, 3.4 g of methylhexahydrophthalic anhydride and 0.05 g of 2-ethyl-4-methylimidazole are uniformly mixed to obtain a prepolymer C;
  • the modified superhydrophobic copper powder is uniformly dispersed on the prepolymer C, and then according to 80 ° C / 2 h + 100 ° C / 2 h + 12 0 Curing at °C/2h+140°C/2h+160°C/4h, after natural cooling, a superhydrophobic electrothermal epoxy resin composite material is obtained, and water droplets are scattered on the surface of the electrothermal epoxy resin composite material.
  • the hemispherical shape indicates that the superhydrophobic electrothermal epoxy resin composite has a good superhydrophobic property similar to that of a lotus leaf.
  • the composite material is approximately 3 in the horizontal direction. Place, apply 10V voltage preheating at both ends, and then place a small amount of crushed ice on the surface. After 27 seconds, the crushed ice can be completely dissolved and automatically slipped from the surface of the composite without any droplets remaining. This phenomenon fully proves that the composite material has a good deicing effect under the joint action of the superhydrophobic surface and the electrothermal intermediate layer, and can be used as a field for deicing and anti-icing of wind power blades.
  • the composite material is approximately 3 in the horizontal direction. Place, apply 10V voltage preheating at both ends, and then place a small amount of crushed ice on the surface. After 27 seconds, the crushed ice can be completely dissolved and automatically slipped from the surface of the composite without any droplets remaining. This phenomenon fully proves that the composite material has a good deicing effect under the joint action of the superhydrophobic surface and the electrothermal intermediate layer, and can be used as a field for deicing and anti-icing of wind power blades.
  • the fracture surface of the fractured superhydrophobic electrothermal epoxy resin composite material is fixed by a clamp and closely adhered, and treated at a temperature of 180 ° C for 3 hours, and the fractured samples can be rejoined together to complete self-repair and composite materials. It still retains its good superhydrophobic properties after self-healing.
  • Prepolymer B was obtained; methyl propionate and ethyl propionate and 1.72 g of untreated single-walled carbon nanotubes were added to prepolymer B, uniformly mixed, and coated in step (2) to obtain reversible Self-repairing epoxy resin, volatilized methyl propionate and ethyl propionate, according to 80 ° C / 2 h + 100 ° C / 2 h + 120 ° C / 2 h + 140 ° C / 2 h + 160 ° C / 4h The process is cured, and after natural cooling, an electrothermal epoxy resin composite material is obtained, with an r g exceeding 110 °C.
  • the prepolymer C is obtained; the prepolymer C is coated on the electrothermal epoxy resin composite material obtained in the step (3), and the modified superhydrophobic copper powder is uniformly dispersed on the prepolymer C, and then 80°. C/2h+100°C /2h+120°C/2h+140°C/2h+160°C/4h process is solidified. After natural cooling, a superhydrophobic electrothermal epoxy resin composite material is obtained. The surface of the electrothermal epoxy composite has a diffuse hemisphere, indicating that the superhydrophobic electrothermal epoxy composite has good superhydrophobic properties similar to those of the lotus leaf.
  • the composite material is approximately 3 in the horizontal direction. Place, apply 10V voltage preheating at both ends, and then place a small amount of crushed ice on the surface. After 26 seconds, the crushed ice can be completely dissolved and automatically slipped from the surface of the composite without any droplets remaining. This phenomenon fully proves that the composite material has a good deicing effect under the joint action of the superhydrophobic surface and the electrothermal intermediate layer, and can be used as a field for deicing and anti-icing of wind power blades.
  • the fracture surface of the fractured superhydrophobic electrothermal epoxy resin composite material is fixed by a clamp and closely adhered, and treated at a temperature of 185 ° C for 1.5 h, and the fractured samples can be rejoined together to complete self-repair and composite.
  • the material retains its good superhydrophobic properties after self-healing.
  • the volatile methyl acetate is cured according to the process of 80 ° C / 2 h + 100 ° C / 2 h + 120 ° C / 2 h + 140 ° C / 2 h + 160 ° C / 4 h, after natural cooling, a kind of Electrothermal epoxy composite, r g exceeds iio°c
  • the prepolymer C is obtained; the prepolymer C is coated on the electrothermal epoxy resin composite material obtained in the step (3), and the modified superhydrophobic copper powder is uniformly dispersed on the prepolymer C, and then 80°. Curing at C/2h+100°C/2h+ 120°C/2h+140°C/2h+160°C/4h, after natural cooling, a superhydrophobic electrothermal epoxy resin composite material is obtained, and the water droplets are heated.
  • the surface of the epoxy resin composite material is in the form of a diffused hemisphere, Mingchao hydrophobic electrothermal epoxy resin composite has good superhydrophobic properties similar to lotus leaf.
  • the composite material was approximately 3 in the horizontal direction. Place, apply 10V voltage preheating at both ends, and then place a small amount of crushed ice on the surface. After 26 seconds, the crushed ice can be completely dissolved and automatically slipped from the surface of the composite without any droplets remaining. This phenomenon fully proves that the composite material has a good deicing effect under the joint action of the superhydrophobic surface and the electrothermal intermediate layer, and can be used as a field for deicing and anti-icing of wind power blades.
  • the fracture surface of the fractured superhydrophobic electrothermal epoxy resin composite material is fixed by a clamp and closely adhered, and treated at a temperature of 175 ° C for 1.3 h, and the fractured samples can be rejoined together to complete self-repair and composite The material retains its good superhydrophobic properties after self-healing.
  • FIG 11 it is a self-repairing digital photo of a superhydrophobic electrothermal epoxy resin composite prepared in Example 1 of the present invention.
  • the original composite material was cut from the middle as a fracture sample, and then the clamped sample was fixed by a clamp and placed in a blast oven at 160 ° C for 1 h.
  • the exchanged samples were rejoined by the exchange reaction of the reversible disulfide bond. Complete self-healing, leaving only a scar on the surface similar to human skin after the wound has healed.
  • FIG. 12 it is a digital photograph of the static contact angle test of the superhydrophobic electrothermal epoxy resin composite prepared in Example 1 of the present invention after self-healing.
  • the surface of the super-hydrophobic electrothermal epoxy resin composite after the water droplets are repaired can still be kept in a nearly spherical shape (Fig. 12a), especially in the scars remaining after self-repair, and the shape of the water droplets is consistent with other parts.
  • the static contact angle of the self-healing surface was 152.0 compared to the original composite. (Fig. 12b), indicating that the composite retains its good superhydrophobic properties after self-healing.
  • 2,2'-dithioglycolic anhydride and methylhexahydrophthalic anhydride are mixed in proportion, added to an epoxy resin, and cured to obtain a reversible self-repairing epoxy resin.
  • the carbon nanotube/epoxy resin prepolymer is uniformly coated and cured to obtain an electrothermal epoxy resin-based composite material; the modified superhydrophobic copper powder is uniformly adhered on the surface of the composite material, and then cured, thereby obtaining an ultra Hydrophobic electrothermal epoxy resin composite.
  • This hair The exchange reaction of the reversible disulfide bond is utilized to simultaneously achieve rapid self-repair of the epoxy resin, the electrothermal layer and the superhydrophobic layer.
  • the electrothermal epoxy resin composite material provided by the invention has reversible self-repairing for major damage such as cracking and peeling, and the heat resistance is outstanding, and exceeds the existing polymer-based reversible self-repairing electrothermal coating.
  • the super-hydrophobic electrothermal epoxy resin composite material provided by the invention can effectively repair major damage such as cracking and peeling, and has good super-hydrophobic effect after repairing.
  • the superhydrophobic electrothermal epoxy resin composite material provided by the invention has the additional reversible self-repairing performance while satisfying the requirements of the wind and ice deicing technology of the wind power blade, and can effectively ensure the operation safety of the wind turbine and prolong the service life.

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Abstract

本发明公开了一种超疏水电热环氧树脂复合材料及其制备与自修复方法。将2,2'-二硫乙二酸酐与甲基六氢邻苯二甲酸酐混合,加入环氧树脂,固化,得到可逆自修复环氧树脂,再涂布碳纳米管/环氧树脂预聚物,固化得到电热环氧树脂基复合材料,再粘附改性超疏水铜粉,固化得到一种超疏水电热环氧树脂复合材料。本发明的电热环氧树脂复合材料对开裂剥离等重大损伤具有可逆自修复的同时,耐热性十分突出,超过现有高分子基可逆自修复电热涂层,可有效修复开裂、剥离等重大损伤,而且修复后仍具有良好的超疏水效果;复合材料在满足风电叶片防冰除冰技术要求的同时,具有额外的可逆自修复性能,可有效保障风电机组的运行安全并延长使用寿命。

Description

一种超疏水电热环氧树脂复合材料及其制备与自修复方 法
技术领域
[0001] 本发明涉及一种超疏水电热环氧树脂复合材料及其制备与自修复方法。
背景技术
[0002] 21世纪, 能源安全与环境保护已经成为全球普遍关注的问题。 风能是清洁能源 中最重要的可再生能源之一, 然而, 全球风电产业每年发生约 3800起风电叶片 损毁事故, 占风力发电机组事故的 40%。 其中, 环氧树脂与上述的功能涂层在长 时间使用中遭受雷击、 暴雪和强风等极端天气后发生开裂与层间剥离是防冰除 冰效果下降和风电叶片损毁的主要原因。
[0003] 显然, 多变的自然气候对风电叶片所使用的环氧树脂与功能涂层的高可靠性提 出了严苛的要求。 近年来, 可逆自修复材料因其具有多次可重复修补物理损伤 与缺陷, 防止材料功能失效和延长材料使用周期的优势, 引起了人们的广泛关 注。 通过总结现有文献报道的基于可逆共价键的环氧树脂可知, 它们的玻璃化 转变温度 (rg) 普遍低于 70°c, 而起始热分解温度 (rdi) 则低于 300°c。 虽然较 低的 rg能保证它们在一定的温度 (RT〜 200°C) 与时间 (0〜 24h) 下实现自修复 , 但是它们较差的耐热性既无法满足作为风电叶片用树脂的要求, 也无法承受 电热涂层除冰时产生的高温。
[0004] 另一方面, 目前已有报道的高分子基可逆自修复电热涂层同样存在耐热性较差 ( rg约为 -120〜 20°c) 的问题。 一旦电热温度超过涂层本身较低的 rg, 在自身 重力的影响下处于橡胶态的涂层有发生大形变的潜在威胁。 而目前自修复超疏 水涂层主要依靠低表面能物质 (长链脂肪烃、 多氟化合物或聚硅氧烷) 的迁移 重排或微胶囊可控释放低表面能物质实现。 这两种修复方式均以超疏水涂层表 面的微纳结构在修复前后保持不变为前提, 仅能实现对轻微摩擦或氧化的自修 复, 对树脂与涂层发生开裂或剥离等重大损伤则无能为力。
[0005] 综上所述, 研发一种兼具良好耐热性与可逆自修复性能的电热超疏水环氧树脂 多层复合材料, 用于修复风电叶片的开裂与层间剥离并保障其防冰除冰效果是 一项具有重大应用价值的课题。
发明概述
技术问题
问题的解决方案
技术解决方案
[0006] 为达到上述目的, 本发明所采用的技术方案是:
[0007] 一种超疏水电热环氧树脂复合材料的制备方法, 包括如下步骤:
[0008] ( 1) 按质量计, 在温度为 50〜 70°C的条件下, 将 100份环氧树脂、 42〜 84份 2, 2 二硫乙二酸酐、 0〜 43份甲基六氢邻苯二甲酸酐混合均匀, 经固化后, 得到可 逆自修复环氧树脂;
[0009] (2) 按质量计, 在温度为 50〜 70°C的条件下, 将 10份环氧树脂、 4.2〜 8.4份 2, 2 二硫乙二酸酐和 0〜 4.3份甲基六氢邻苯二甲酸酐混合均匀, 得到预聚物; 向预 聚物中加入酯溶剂和 0.1〜 4份碳纳米管, 混合均匀得到涂布物; 然后将涂布物涂 布在步骤 ( 1) 制得的可逆自修复环氧树脂上, 经挥发酯溶剂、 固化后, 得到电 热环氧树脂复合材料;
[0010] (3) 按质量计, 将 4份纳米铜粉与 0.1〜 2份全氟羧酸分散在水中, 混合均匀后 静置、 过滤、 干燥, 得到改性超疏水铜粉;
[0011] (4) 按质量计, 在温度为 50〜 70°C的条件下, 将 10份环氧树脂、 4.2〜 8.4份 2, 2 二硫乙二酸酐、 0〜 4.3份甲基六氢邻苯二甲酸酐混合均勻, 得到混合物; 将混 合物、 改性超疏水铜粉依次设置在步骤 (2) 制得的电热环氧树脂复合材料上, 固化后, 得到超疏水电热环氧树脂复合材料。
[0012] 本发明还公开了一种电热环氧树脂复合材料的制备方法, 包括如下步骤:
[0013] ( 1) 按质量计, 在温度为 50〜 70°C的条件下, 将 100份环氧树脂、 42〜 84份 2, 2 二硫乙二酸酐、 0〜 43份甲基六氢邻苯二甲酸酐混合均匀, 经固化后, 得到可 逆自修复环氧树脂;
[0014] (2) 按质量计, 在温度为 50〜 70°C的条件下, 将 10份环氧树脂、 4.2〜 8.4份 2, 2 二硫乙二酸酐和 0〜 4.3份甲基六氢邻苯二甲酸酐混合均匀, 得到预聚物; 向预 聚物中加入酯溶剂和 0.1〜 4份碳纳米管, 混合均匀得到涂布物; 然后将涂布物涂 布在步骤 ( 1) 制得的可逆自修复环氧树脂上, 经挥发酯溶剂、 固化后, 得到电 热环氧树脂复合材料。
[0015] 优选的, 所述 2,2’-二硫乙二酸酐的制备方法如下:
[0016] ( 1) 按质量计, 在温度为 20〜 30°C的条件下, 将 120份 2 -巯基乙酸、 500〜 700 份酯类溶剂和 0.6〜 1.2份碘化钾混合均匀, 形成溶液; 缓慢向溶液中加入 80〜 90 份浓度为 30wt%的双氧水后, 保温反应 2〜 4h, 得到 2,2’-二硫乙二酸;
[0017] (2) 按质量计, 在温度为 20〜 30°C和搅拌条件下, 将 100份 2,2’-二硫乙二酸和
120〜 150份酸酐混合并保温反应 2〜 4h, 得到 2,2’-二硫乙二酸酐。
[0018] 上述技术方案中, 所述酯溶剂、 酯类溶剂独立的选自乙酸甲酯、 乙酸乙酯、 乙 酸丙酯、 丙酸甲酯、 丙酸乙酯的一种或几种。
[0019] 上述技术方案中, 所述全氟羧酸为全氟辛酸、 全氟壬酸、 全氟癸酸中的一种或 几种。
[0020] 上述技术方案中, 所述环氧树脂为缩水甘油醚型环氧树脂、 缩水甘油酯型环氧 树脂、 缩水甘油胺型环氧树脂、 脂肪族环氧化合物、 脂环族环氧化合物中的一 种, 或它们的任意组合; 所述碳纳米管为未经表面处理的单壁碳纳米管、 多壁 碳纳米管中的一种, 或它们的任意组合。
[0021] 上述技术方案中, 所述酸酐为乙酸酐、 三氟乙酸酐中的一种, 或它们的任意组 合。
[0022] 本发明公开了上述超疏水电热环氧树脂复合材料的制备方法制备的超疏水电热 环氧树脂复合材料; 或者上述电热环氧树脂复合材料的制备方法制备的电热环 氧树脂复合材料。
[0023] 本发明还公开了 2,2’-二硫乙二酸酐在制备上述超疏水电热环氧树脂复合材料或 者上述电热环氧树脂复合材料中的应用。
[0024] 本发明进一步公开了上述超疏水电热环氧树脂复合材料的自修复方法, 包括以 下步骤, 将受损超疏水电热环氧树脂复合材料的断面用夹具固定并紧密贴合, 在温度为 160〜 200°C的条件下处理 1〜 3小时, 完成超疏水电热环氧树脂复合材料 的自修复。 [0025] 本发明进一步公开了上述电热环氧树脂复合材料的自修复方法, 包括以下步骤 , 将受损电热环氧树脂复合材料的断面用夹具固定并紧密贴合, 在温度为 160〜 200°C的条件下处理 1〜 3小时, 完成电热环氧树脂复合材料的自修复。
发明的有益效果
有益效果
[0026] 本发明提供的电热环氧树脂复合材料对开裂剥离等重大损伤具有可逆自修复性 會 L 同时环氧树脂本身较大的刚性与较高的交联密度使复合材料具有突出的耐 热性 (r=ii3°c) , 超过现有高分子基可逆自修复电热涂层。 本发明提供的超 疏水电热环氧树脂复合材料借助树脂层中的可逆二硫醚键的交换反应, 自下而 上带动超疏水层的修复, 因此可有效修复开裂剥离等重大损伤且修复后仍具有 良好的超疏水效果。 本发明提供的超疏水电热环氧树脂复合材料在满足风电叶 片防冰除冰技术要求的同时, 具有额外的可逆自修复性能, 可有效保障风电机 组的运行安全并延长使用寿命。
对附图的简要说明
附图说明
[0027] 图 1是实施例 1提供的 2,2’-二硫乙二酸酐的合成流程示意图 (反应式) 。
[0028] 图 2是实施例 1制备的产物的核磁共振氢谱 OH-NMR) 。
[0029] 图 3是实施例 1制备的可逆自修复环氧树脂与电热环氧树脂复合材料的红外谱图
[0030] 图 4是实施例 1的可逆自修复环氧树脂与电热环氧树脂复合材料的动态力学曲线
[0031] 图 5是实施例 1制备的电热环氧树脂复合材料的静接触角测试数码照片。
[0032] 图 6是实施例 1制备的改性超疏水铜粉的红外谱图。
[0033] 图 7是实施例 1制备的改性超疏水铜粉的 X射线衍射谱图。
[0034] 图 8是实施例 1制备的超疏水电热环氧树脂复合材料的静接触角测试数码照片。
[0035] 图 9是实施例 1制备的超疏水电热环氧树脂复合材料的电热近红外成像数码照片
[0036] 图 10是实施例 1制备的超疏水电热环氧树脂复合材料的电热除冰数码照片。 [0037] 图 11是实施例 9制备的超疏水电热环氧树脂复合材料的自修复效果数码照片。
[0038] 图 12是实施例 9的超疏水电热环氧树脂复合材料自修复后的静接触角照片。
发明实施例
本发明的实施方式
[0039] 实施例 1
[0040] 1) 2,2’-二硫乙二酸酐的制备
[0041] 按照附图 1所示的合成反应式合成。 具体步骤如下: 按质量计, 在温度为 20°C 的条件下, 将 120g
2 -巯基乙酸、 500g乙酸乙酯和 0.6g碘化钾混合均匀, 形成溶液 A; 缓慢向溶液 A 中加入 80g浓度为 30wt%的双氧水后, 保温反应 2h; 反应结束后, 所得溶液经 300 mL饱和亚硫酸钠溶液洗涤、 减压蒸除乙酸乙酯后, 得到 2,2’-二硫乙二酸, 其核 磁共振氢谱见附图 2。
[0042] 按质量计, 在温度为 20°C和搅拌条件下, 将 100g 2,2’-二硫乙二酸和 150g三氟乙 酸酐混合并保温 2h; 所得溶液减压蒸除过量三氟乙酸酐与生成的三氟乙酸, 即 得到 2,2’-二硫乙二酸酐, 其核磁共振氢谱见附图 2。
[0043] 2) 可逆自修复环氧树脂的制备
[0044] 按质量计, 在温度为 50°C的条件下, 将 100g缩水甘油醚型环氧树脂 (牌号: E5 1, 环氧当量: 196g/eq) 、 42g的 2,2’-二硫乙二酸酐、 43g甲基六氢邻苯二甲酸酐 和 0.5g2 -乙基 -4 -甲基咪唑混合均匀, 而后按照 80°C/2h+100°C/2h+120°C/2h+140°C/ 2h+160°C/4h的工艺进行固化, 自然冷却后脱模, 得到一种可逆自修复环氧树脂 ; 其红外谱图、 动态力学曲线分别见附图 3、 4。
[0045] 3) 电热环氧树脂复合材料的制备
[0046] 按质量计, 在温度为 50°C的条件下, 将 10g缩水甘油醚型环氧树脂 (牌号: E51 , 环氧当量: 196g/eq) 、 4.2g
2,2’-二硫乙二酸酐、 4.3g甲基六氢邻苯二甲酸酐和 0.05g 2 -乙基 -4 -甲基咪唑混合 均匀, 得到预聚物 B ; 向预聚物 B中加入乙酸乙酯和 2.07g未经表面处理的多壁碳 纳米管, 混合均匀, 涂布在步骤 (2) 制得的可逆自修复环氧树脂上, 挥发乙酸 乙酯, 然后按照 80。(:/211+100。(:/211+120。(:/211+140。(:/211+160。(:/411的工艺进行固化 , 自然冷却后, 得到一种电热环氧树脂复合材料; 其红外谱图、 动态力学曲线 和静接触角测试数码照片分别见附图 3、 4和 5。
[0047] 4) 改性超疏水铜粉的制备
[0048] 按质量计, 将 4g纳米铜粉与 0.8g全氟癸酸分散在水中, 混合均匀后静置、 过滤 , 水洗滤饼后烘干, 得到改性超疏水铜粉, 其红外谱图、 X射线衍射谱图分别见 附图 6和 7。
[0049] 5) 超疏水电热环氧树脂复合材料的制备
[0050] 按质量计, 在温度为 50°C的条件下, 将 10g缩水甘油醚型环氧树脂 (牌号: E51 , 环氧当量: 196g/eq) 、 4.2g
2,2’-二硫乙二酸酐、 4.3g甲基六氢邻苯二甲酸酐和 0.05g 2 -乙基 -4 -甲基咪唑混合 均匀, 得到预聚物 C; 将预聚物 C涂布在步骤 (3) 制得的电热环氧树脂复合材料 上, 再将改性超疏水铜粉均匀分散在预聚物 C上, 而后按照 80°C/2h+100°C/2h+12 0°C/2h+140°C/2h+160°C/4h的工艺进行固化, 自然冷却后, 得到一种超疏水电热 环氧树脂复合材料; 其静接触角测试、 电热近红外成像和电热除冰的数码照片 分别见附图 8、 9和 10。
[0051] 参见附图 1, 它是本发明实施例 1提供的 2,2’-二硫乙二酸酐的合成流程示意图 ( 反应式) 。 第一步为硫醇键的氧化反应, 生成具有可逆特性的二硫醚键; 第二 步为羧基的脱水缩合反应, 生成酸酐, 可用于与环氧基的固化反应。
[0052] 参见附图 2, 它是本发明实施例 1制备的 2,2’ -二硫乙二酸和 2, 2’ -二硫乙二酸酐的 核磁共振氢谱 ( -NMR) 。 相比于起始化合物 2 -巯基乙酸的谱图, 2,2’-二硫乙 二酸的 iH-NMR中没有出现巯基 H的特征峰 (2.78ppm) , 说明巯基经过双氧水 氧化生成了二硫醚键; 而经过缩合反应后, 羧基 H (I2.75ppm) 未出现在 2,2’-二 硫乙二酸酐的 iH-NMR中, 说明 2,2’-二硫乙二酸中的羧基已经缩合生成酸酐。
[0053] 参见附图 3, 它是本发明实施例 1制备的可逆自修复环氧树脂与电热环氧树脂复 合材料的红外谱图。 其中 2800至 3000cm - 1之间的伸缩振动峰归属于 -CH 3 (2960cm - 1和 2870cm -1) 和 -CH 2 - (2920cm - 1和 2850cm -1) , 1730cm - 1处的尖锐 峰为酯基中 C=0的伸缩振动峰, 而 1412cm -1
处的吸收峰为 2, 2’ -二硫乙二酸酐中的 C-S的特征峰, 说明 2,2’ -二硫乙二酸酐已融 入环氧树脂的交联结构中; 而在 910cm -i与 845cm -i附近并无明显环氧基特征峰, 则表明环氧树脂中的环氧基已经与固化剂反应完全。
[0054] 参见附图 4, 它是本发明实施例 1制备的可逆自修复环氧树脂与电热环氧树脂复 合材料的动态力学曲线。 其中, 以介质损耗角正切 (tan6) 的峰顶温度作为树脂 与复合材料的 7> 可逆自修复环氧树脂的动态力学曲线呈现单一的 tan6峰, 其 g 约为 113°C。 在可逆自修复环氧树脂中加入碳纳米管后, 电热环氧树脂复合材料 的动态力学曲线在 100°C附近出现一肩峰。 显然, 肩峰的出现是环氧树脂聚合物 链在碳纳米管表面缠结形成树脂 /填料过度层产生的。 同时, 电热环氧树脂复合 材料的 tan6的峰高低于可逆自修复环氧树脂的峰高, 这说明碳纳米管对分子链运 动具有阻碍作用。 值得一提的是, 以往报道的可逆自修复电热复合材料的绝大 多数为水凝胶和弹性体, g普遍低于 20°C, 主要应用领域为传感器与可穿戴器 件。 本发明制备的电热环氧树脂复合材料的 7%则为 113°C。 很显然, 较高的 rg更 能使电热环氧树脂复合材料具备较好的耐热性, 足以承受通电后材料产生的焦 耳热, 对保持风电叶片的三维尺寸具有重要意义。
[0055] 参见附图 5, 它是本发明实施例 1制备的电热环氧树脂复合材料的静接触角测试 数码照片。 如图 5a所示, 水滴在电热环氧树脂复合材料的表面呈散开的半球状, 而相应的静态接触角为 89.5。。
[0056] 参见附图 6, 它是本发明实施例 1制备的改性超疏水铜粉的红外谱图。 其中, 16 60cm -1处和 1464至 1413cm -1处的谱带分别是全氟癸酸中羧酸根的不对称伸缩振动 和对称伸缩振动峰; 而 1360cm -1和 1317cm - 1处的谱带属于全氟癸酸中 CF 3的伸缩 振动峰, 1198cm - 1和 1140cm - 1处的谱带则是全氟癸酸中 CF ^伸缩振动峰。 这一 结果说明铜粉经过改性后已被 CF 2mcF 3基团包裹, 具有较低的表面能。
[0057] 参见附图 7, 它是本发明实施例 1制备的改性超疏水铜粉的 X射线衍射谱图。 其 中, 29.48。, 36.34。, 42.39。和 61.43。处的衍射峰为 Cu 20的特征峰, 而 43.28。
, 50.38。, 74.12。和 89.90。处的衍射峰为 Cu的特征峰。 Cu 2
0的来源可能是部分 Cu与氧气发生反应所得。
[0058] 参见附图 8, 它是本发明实施例 1制备的超疏水电热环氧树脂复合材料的静接触 角测试数码照片。 当电热环氧树脂复合材料表面均匀粘附了一层改性超疏水铜 粉并经过固化后, 水滴在所得到的超疏水电热环氧树脂复合材料表面的形态转 变为近似圆球状 (图 8a) , 其表面的静态接触角增大至 154.0。 (图 8b) 。 超疏水 电热环氧树脂复合材料表面滑落角测试的视频截图如图 8c所示, 当复合材料的滑 动角约为 3。时, 水滴在材料表面可迅速滚落。 以上结果表明, 超疏水电热环氧 树脂复合材料具有类似于荷叶的良好超疏水性能。
[0059] 参见附图 9, 它是本发明实施例 1制备的超疏水电热环氧树脂复合材料的电热近 红外成像数码照片。 通过调节电压即可有效调控复合材料的加热温度。 根据焦 耳定律, 超疏水电热环氧树脂复合材料的加热温度随着电压的增大逐渐升高。 当所加电压为 15V时, 复合材料的最高温度稳定在 96.7°C, 低于可逆自修复环氧 树脂与电热环氧树脂复合材料的 g (113°C) , 复合材料良好的耐热性可有效保 证其在加热除冰时自身的尺寸稳定和使用安全。
[0060] 参见附图 10, 它是本发明实施例 1制备的超疏水电热环氧树脂复合材料的电热 除冰数码照片。 将复合材料与水平方向大约呈 3。放置, 两端施加 10V电压预热, 随后在其表面放置少量碎冰, 经过 26秒后, 碎冰可完全溶解并从复合材料表面 自动滑落, 且无液滴残留。 这一现象充分证明复合材料在超疏水表面与电热中 间层的共同作用下具有良好的除冰效果, 可用作风电叶片除冰防冰领域。
[0061] 实施例 2
[0062] 具体步骤如下: 按质量计, 在温度为 25°C的条件下, 将 120g 2 -巯基乙酸、 600g 乙酸甲酯和 0.8g碘化钾混合均匀, 形成溶液 A; 缓慢向溶液 A中加入 85g浓度为 30 wt%的双氧水后, 保温反应 3h; 反应结束后, 所得溶液经 300 mL饱和亚硫酸钠 溶液洗涤、 减压蒸除乙酸甲酯后, 得到 2,2’-二硫乙二酸。
[0063] 按质量计, 在温度为 25°C和搅拌条件下, 将 100g 2,2’-二硫乙二酸和 135g乙酸酐 混合并保温 3h; 所得溶液减压蒸除过量乙酸酐与生成的乙酸后, 得到 2,2’-二硫乙 二酸酐。
[0064] 按质量计, 在温度为 60°C的条件下, 100g缩水甘油酯型环氧树脂 (牌号: 672 , 环氧当量: 161g/eq) 、 65g
2,2’-二硫乙二酸酐、 15g甲基六氢邻苯二甲酸酐和 0.5g 2 -乙基 -4 -甲基咪唑混合均 匀, 而后按照 80°C/2h+100°C/2h+120°C/2h+140°C/2h+160°C/4h的工艺进行固化, 自然冷却后脱模, 得到一种可逆自修复环氧树脂。
[0065] 按质量计, 在温度为 60°C的条件下, 将 10g缩水甘油酯型环氧树脂 (牌号: 672 , 环氧当量: 161g/eq) 、 6.5g
2,2’-二硫乙二酸酐、 1.5g甲基六氢邻苯二甲酸酐和 0.05g 2 -乙基 -4 -甲基咪唑混合 均匀, 得到预聚物 B ; 向预聚物 B中加入乙酸甲酯和 1.06g未经表面处理的单壁碳 纳米管, 混合均匀, 涂布在步骤 (2) 制得的可逆自修复环氧树脂上, 经挥发乙 酸甲酯, 按照 80°C/2h+100°C/2h+120°C/2h+140°C/2h+160°C/4h的工艺进行固化, 自然冷却后, 得到一种电热环氧树脂复合材料, rg超过 iio°c
[0066] 按质量计, 将 4g纳米铜粉与 O.lg全氟辛酸分散在水中, 混合均匀后静置、 过滤 , 水洗滤饼后烘干, 得到改性超疏水铜粉。
[0067] 按质量计, 在温度为 60°C的条件下, 将 10g缩水甘油酯型环氧树脂 (牌号: 672 , 环氧当量: 161 g/eq) 、 6.5g 2,2’-二硫乙二酸酐、 1.5g甲基六氢邻苯二甲酸酐 和 0.05g 2 -乙基 -4 -甲基咪唑混合均匀, 得到预聚物 C; 将预聚物 C涂布在步骤 (3 ) 制得的电热环氧树脂复合材料上, 再将改性超疏水铜粉均匀分散在预聚物 C上 , 而后按照 80°C/2h+100°C/2h+120°C/2h+140°C/2h+160°C/4h的工艺进行固化, 自 然冷却后, 得到一种超疏水电热环氧树脂复合材料, 水滴在电热环氧树脂复合 材料的表面呈散开的半球状, 表明超疏水电热环氧树脂复合材料具有类似于荷 叶的良好超疏水性能。
[0068] 将复合材料与水平方向大约呈 3。放置, 两端施加 10V电压预热, 随后在其表面 放置少量碎冰, 经过 26秒, 碎冰可完全溶解并从复合材料表面自动滑落, 且无 液滴残留。 这一现象充分证明复合材料在超疏水表面与电热中间层的共同作用 下具有良好的除冰效果, 可用作风电叶片除冰防冰领域。
[0069] 超疏水电热环氧树脂复合材料的自修复方法
[0070] 将断裂的超疏水电热环氧树脂复合材料的断面处用夹具固定并紧密贴合, 在温 度为 180°C的条件下处理 2h, 断裂样品可重新连接在一起完成自修复且复合材料 在自修复后仍然保持了其良好的超疏水性能。
[0071] 实施例 3
[0072] 具体步骤如下: 按质量计, 在温度为 30°C的条件下, 将 120g 2 -巯基乙酸、 700g 乙酸丙酯和 l.Og碘化钾混合均匀, 形成溶液 A; 缓慢向溶液 A中加入 90g浓度为 30 wt%的双氧水后, 保温反应 4h; 反应结束后, 所得溶液经 300 mL饱和亚硫酸钠 溶液洗涤、 减压蒸除乙酸丙酯后, 得到 2,2’-二硫乙二酸。
[0073] 按质量计, 在温度为 30°C和搅拌条件下, 将 100g 2,2’-二硫乙二酸和 120g乙酸酐 混合并保温 4h; 所得溶液减压蒸除过量乙酸酐与生成的乙酸后, 得到 2,2’-二硫乙 二酸酐。
[0074] 按质量计, 在温度为 70°C的条件下, 100g缩水甘油胺型环氧树脂 (牌号: AFG -90, 环氧当量: 118g/eq) 、 55g 2,2’-二硫乙二酸酐、 25g甲基六氢邻苯二甲酸酐 和 0.5g
2 -乙基 -4 -甲基咪唑混合均匀, 而后按照 80°C/2h+100°C/2h+120°C/2h+140°C/2h+16 0°C/4h的工艺进行固化, 自然冷却后脱模, 得到一种可逆自修复环氧树脂。
[0075] 按质量计, 在温度为 70°C的条件下, 将 10g缩水甘油胺型环氧树脂 (牌号: AF G-90, 环氧当量: 118g/eq) 、 5.5g 2,2’-二硫乙二酸酐、 2.5g甲基六氢邻苯二甲酸 酐和 0.05g 2 -乙基 -4 -甲基咪唑混合均匀, 得到预聚物 B ; 向预聚物 B中加入丙酸甲 酯、 1.04g未经表面处理的单壁碳纳米管和 1.04g未经表面处理的多壁碳纳米管, 混合均匀, 涂布在步骤 (2) 制得的可逆自修复环氧树脂上, 经挥发丙酸甲酯, 按照 80°C/2h+100°C/2h+120°C/2h+140°C/2h+160°C/4h的工艺进行固化, 自然冷却 后, 得到电热环氧树脂复合材料, rg超过 iio°c
[0076] 按质量计, 将 4g纳米铜粉与 2.1g全氟壬酸分散在水中, 混合均匀后静置、 过滤 , 水洗滤饼后烘干, 得到改性超疏水铜粉。
[0077] 按质量计, 在温度为 70°C的条件下, 将 10g缩水甘油胺型环氧树脂 (牌号: AF G-90, 环氧当量: 118g/eq) 、 5.5g 2,2’-二硫乙二酸酐、 2.5g甲基六氢邻苯二甲酸 酐和 0.05g
2 -乙基 _4 -甲基咪唑混合均匀, 得到预聚物 C; 将预聚物 C涂布在步骤 (3) 制得的 电热环氧树脂复合材料上, 再将改性超疏水铜粉均匀分散在预聚物 C上, 而后按 照 80°C/2h+100°C/2h+120°C/2h+140°C/2h+160°C/4h的工艺进行固化, 自然冷却后 , 得到一种超疏水电热环氧树脂复合材料, 水滴在电热环氧树脂复合材料的表 面呈散开的半球状, 表明超疏水电热环氧树脂复合材料具有类似于荷叶的良好 超疏水性能。
[0078] 将复合材料与水平方向大约呈 3。放置, 两端施加 10V电压预热, 随后在其表面 放置少量碎冰, 经过 27秒, 碎冰可完全溶解并从复合材料表面自动滑落, 且无 液滴残留。 这一现象充分证明复合材料在超疏水表面与电热中间层的共同作用 下具有良好的除冰效果, 可用作风电叶片除冰防冰领域。
[0079] 超疏水电热环氧树脂复合材料的自修复方法
[0080] 将断裂的超疏水电热环氧树脂复合材料的断面处用夹具固定并紧密贴合, 在温 度为 200°C的条件下处理 3h, 断裂样品可重新连接在一起完成自修复且复合材料 在自修复后仍然保持了其良好的超疏水性能。
[0081] 实施例 4
[0082] 具体步骤如下: 按质量计, 在温度为 25°C的条件下, 将 120g 2 -巯基乙酸、 500g 丙酸甲酯和 1.2g碘化钾混合均匀, 形成溶液 A; 缓慢向溶液 A中加入 85g浓度为 30 wt%的双氧水后, 保温反应 2.5h; 反应结束后, 所得溶液经 300 mL饱和亚硫酸钠 溶液洗涤、 减压蒸除丙酸甲酯后, 得到 2,2’-二硫乙二酸。
[0083] 按质量计, 在温度为 25°C和搅拌条件下, 将 100g 2,2’-二硫乙二酸和 75g乙酸酐 与 75g三氟乙酸酐混合并保温 2.5h; 所得溶液减压蒸除过量酸酐与生成的羧酸后 , 得到 2,2’-二硫乙二酸酐。
[0084] 按质量计, 在温度为 70°C的条件下, 100g脂肪族环氧化合物 (牌号: EPG-205 , 环氧当量: 178g/eq) 、 44g
2,2’-二硫乙二酸酐、 41g甲基六氢邻苯二甲酸酐和 0.5g 2 -乙基 -4 -甲基咪唑混合均 匀, 而后按照 80°C/2h+100°C/2h+120°C/2h+140°C/2h+160°C/4h的工艺进行固化, 自然冷却后脱模, 得到一种可逆自修复环氧树脂。
[0085] 按质量计, 在温度为 70°C的条件下, 将 10g脂肪族环氧化合物 (牌号: EPG-205 , 环氧当量: 178g/eq) 、 4.4g
2,2’-二硫乙二酸酐、 4.1g甲基六氢邻苯二甲酸酐和 0.05g 2 -乙基 -4 -甲基咪唑混合 均匀, 得到预聚物 B ; 向预聚物 B中加入丙酸乙酯和 2.01g未经表面处理的多壁碳 纳米管, 混合均匀, 涂布在步骤 (2) 制得的可逆自修复环氧树脂上, 经挥发丙 酸乙酯, 按照 80。(:/211+100。(:/211+120。(:/211+140。(:/211+160。(:/411的工艺进行固化, 自然冷却后, 得到一种电热环氧树脂复合材料, rg超过 iio°c
[0086] 按质量计, 将 4g纳米铜粉与 0.8g全氟癸酸和 0.8g全氟辛酸分散在水中, 混合均 匀后静置、 过滤, 水洗滤饼后烘干, 得到改性超疏水铜粉。
[0087] 按质量计, 在温度为 70°C的条件下, 将 10g脂肪族环氧化合物 (牌号: EPG-205 , 环氧当量: 178g/eq) 、 4.4g
2,2’-二硫乙二酸酐、 4.1g甲基六氢邻苯二甲酸酐和 0.05g 2 -乙基 -4 -甲基咪唑混合 均匀, 得到预聚物 C; 将预聚物 C涂布在步骤 (3) 制得的电热环氧树脂复合材料 上, 再将改性超疏水铜粉均匀分散在预聚物 C上, 而后按照 80°C/2h+100°C/2h+12 0°C/2h+140°C/2h+160°C/4h的工艺进行固化, 自然冷却后, 得到一种超疏水电热 环氧树脂复合材料, 水滴在电热环氧树脂复合材料的表面呈散开的半球状, 表 明超疏水电热环氧树脂复合材料具有类似于荷叶的良好超疏水性能。
[0088] 将复合材料与水平方向大约呈 3。放置, 两端施加 10V电压预热, 随后在其表面 放置少量碎冰, 经过 26秒, 碎冰可完全溶解并从复合材料表面自动滑落, 且无 液滴残留。 这一现象充分证明复合材料在超疏水表面与电热中间层的共同作用 下具有良好的除冰效果, 可用作风电叶片除冰防冰领域。
[0089] 超疏水电热环氧树脂复合材料的自修复方法
[0090] 将断裂的超疏水电热环氧树脂复合材料的断面处用夹具固定并紧密贴合, 在温 度为 160°C的条件下处理 2h, 断裂样品可重新连接在一起完成自修复且复合材料 在自修复后仍然保持了其良好的超疏水性能。
[0091] 实施例 5
[0092] 具体步骤如下: 按质量计, 在温度为 25°C的条件下, 将 120g 2 -巯基乙酸、 600g 丙酸乙酯和 0.7g碘化钾混合均匀, 形成溶液 A; 缓慢向溶液 A中加入 85g浓度为 30 wt%的双氧水后, 保温反应 2h; 反应结束后, 所得溶液经 300 mL饱和亚硫酸钠 溶液洗涤、 减压蒸除丙酸乙酯后, 得到 2,2’-二硫乙二酸。
[0093] 按质量计, 在温度为 25°C和搅拌条件下, 将 100g 2,2’-二硫乙二酸和 150g三氟乙 酸酐混合并保温 2h; 所得溶液减压蒸除过量三氟乙酸酐与生成的三氟乙酸后, 得到 2,2’-二硫乙二酸酐。
[0094] 按质量计, 在温度为 50°C的条件下, 100g脂环族环氧化合物 (牌号: H71, 环 氧当量: 154g/eq) 、 51g 2,2’-二硫乙二酸酐、 34g甲基六氢邻苯二甲酸酐和 0.5g 2 -乙基 -4 -甲基咪唑混合均匀, 而后按照 80°C/2h+100°C/2h+120°C/2h+140°C/2h+16 0°C/4h的工艺进行固化, 自然冷却后脱模, 得到一种可逆自修复环氧树脂。
[0095] 按质量计, 在温度为 50°C的条件下, 将 10g脂环族环氧化合物 (牌号: H71, 环 氧当量: 154g/eq) 、 5.1g
2,2’-二硫乙二酸酐、 3.4g甲基六氢邻苯二甲酸酐和 0.05g 2 -乙基 -4 -甲基咪唑混合 均匀, 得到预聚物 B ; 向预聚物 B中加入乙酸乙酯与乙酸甲酯和 1.09g未经表面处 理的单壁碳纳米管, 混合均匀, 涂布在步骤 (2) 制得的可逆自修复环氧树脂上
, 经挥发乙酸乙酯与乙酸甲酯, 按照 80°C/2h+100°C/2h+120°C/2h+140°C/2h+160 °c/4h的工艺进行固化, 自然冷却后, 得到一种电热环氧树脂复合材料, rg 超过 110°C。
[0096] 按质量计, 将 4g纳米铜粉与 0.8g全氟癸酸和 l.Og全氟壬酸分散在水中, 混合均 匀后静置、 过滤, 水洗滤饼后烘干, 得到改性超疏水铜粉。
[0097] 按质量计, 在温度为 50°C的条件下, 将 10g脂环族环氧化合物 (牌号: H71, 环 氧当量: 154g/eq) 、 5.1g
2,2’-二硫乙二酸酐、 3.4g甲基六氢邻苯二甲酸酐和 0.05g 2 -乙基 -4 -甲基咪唑混合 均匀, 得到预聚物 C; 将预聚物 C涂布在步骤 (3) 制得的电热环氧树脂复合材料 上, 再将改性超疏水铜粉均匀分散在预聚物 C上, 而后按照 80°C/2h+100°C/2h+12 0°C/2h+140°C/2h+160°C/4h的工艺进行固化, 自然冷却后, 得到一种超疏水电热 环氧树脂复合材料, 水滴在电热环氧树脂复合材料的表面呈散开的半球状, 表 明超疏水电热环氧树脂复合材料具有类似于荷叶的良好超疏水性能。
[0098] 将复合材料与水平方向大约呈 3。放置, 两端施加 10V电压预热, 随后在其表面 放置少量碎冰, 经过 27秒, 碎冰可完全溶解并从复合材料表面自动滑落, 且无 液滴残留。 这一现象充分证明复合材料在超疏水表面与电热中间层的共同作用 下具有良好的除冰效果, 可用作风电叶片除冰防冰领域。
[0099] 超疏水电热环氧树脂复合材料的自修复方法
[0100] 将断裂的超疏水电热环氧树脂复合材料的断面处用夹具固定并紧密贴合, 在温 度为 175°C的条件下处理 lh, 断裂样品可重新连接在一起完成自修复且复合材料 在自修复后仍然保持了其良好的超疏水性能。
[0101] 实施例 6
[0102] 具体步骤如下: 按质量计, 在温度为 23°C的条件下, 将 120g 2 -巯基乙酸、 250g 乙酸乙酯和 250g乙酸丙酯及 0.6g碘化钾混合均匀, 形成溶液 A; 缓慢向溶液 A中 加入 83g浓度为 30wt%的双氧水后, 保温反应 3h; 反应结束后, 所得溶液经 300 mL饱和亚硫酸钠溶液洗涤、 减压蒸除乙酸乙酯和乙酸丙酯后, 得到 2,2’-二硫乙 二酸。
[0103] 按质量计, 在温度为 23°C和搅拌条件下, 将 100g 2,2’-二硫乙二酸和 140g三氟乙 酸酐混合并保温 2h; 所得溶液减压蒸除过量三氟乙酸酐与生成的三氟乙酸后, 得到 2,2’-二硫乙二酸酐。
[0104] 按质量计, 在温度为 50°C的条件下, 将 50g缩水甘油醚型环氧树脂 (牌号: E51 , 环氧当量: 196g/eq) 和 50g缩水甘油酯型环氧树脂 (牌号: 672, 环氧当量: 1 61g/eq) 、 44g 2,2’-二硫乙二酸酐、 41g甲基六氢邻苯二甲酸酐和 0.5g 2 -乙基 -4 -甲 基咪唑混合均匀, 而后按照 80°C/2h+100°C/2h+120°C/2h+140°C/2h+160°C/4h的工 艺进行固化, 自然冷却后脱模, 得到一种可逆自修复环氧树脂。
[0105] 按质量计, 在温度为 50°C的条件下, 将 5g缩水甘油醚型环氧树脂 (牌号: E51 , 环氧当量: 196g/eq) 和 5g缩水甘油酯型环氧树脂 (牌号: 672, 环氧当量: 16 lg/eq) 、 4.4g 2,2’-二硫乙二酸酐、 4.1g甲基六氢邻苯二甲酸酐和 0.05g 2 -乙基 -4- 甲基咪唑混合均匀, 得到预聚物 B ; 向预聚物 B中加入乙酸甲酯和丙酸甲酯和 1.1 7g未经表面处理的多壁碳纳米管, 混合均匀, 涂布在步骤 (2) 制得的可逆自修 复环氧树脂上, 经挥发乙酸甲酯和丙酸甲酯, 按照 80°C/2h+100°C/2h+120°C/2h+l 40°C/2h+160°C/4h的工艺进行固化, 自然冷却后, 得到一种电热环氧树脂复合材 料, g超过 110°C。
[0106] 按质量计, 将 4g纳米铜粉与 0.6g全氟辛酸和 0.2g全氟壬酸分散在水中, 混合均 匀后静置、 过滤, 水洗滤饼后烘干, 得到改性超疏水铜粉。
[0107] 按质量计, 在温度为 50°C的条件下, 将 5g缩水甘油醚型环氧树脂 (牌号: E51 , 环氧当量: 196g/eq) 和 5g缩水甘油酯型环氧树脂 (牌号: 672, 环氧当量: 16 lg/eq) 、 4.4g 2,2’-二硫乙二酸酐、 4.1g甲基六氢邻苯二甲酸酐和 0.05g 2 -乙基 -4 - 甲基咪唑混合均匀, 得到预聚物 C; 将预聚物 C涂布在步骤 (3) 制得的电热环氧 树脂复合材料上, 再将改性超疏水铜粉均匀分散在预聚物 C上, 而后按照 80°C/2h +100°C/2h+120°C/2h+140°C/2h+160°C/4h的工艺进行固化, 自然冷却后, 得到一 种超疏水电热环氧树脂复合材料, 水滴在电热环氧树脂复合材料的表面呈散开 的半球状, 表明超疏水电热环氧树脂复合材料具有类似于荷叶的良好超疏水性 能。
[0108] 将复合材料与水平方向大约呈 3。放置, 两端施加 10V电压预热, 随后在其表面 放置少量碎冰, 经过 27秒, 碎冰可完全溶解并从复合材料表面自动滑落, 且无 液滴残留。 这一现象充分证明复合材料在超疏水表面与电热中间层的共同作用 下具有良好的除冰效果, 可用作风电叶片除冰防冰领域。
[0109] 超疏水电热环氧树脂复合材料的自修复方法
[0110] 将断裂的超疏水电热环氧树脂复合材料的断面处用夹具固定并紧密贴合, 在温 度为 180°C的条件下处理 3h, 断裂样品可重新连接在一起完成自修复且复合材料 在自修复后仍然保持了其良好的超疏水性能。
[0111] 实施例 7
[0112] 具体步骤如下: 按质量计, 在温度为 25°C的条件下, 将 120g 2 -巯基乙酸、 250g 乙酸甲酯和 350g丙酸甲酯及 l. lg碘化钾混合均匀, 形成溶液 A; 缓慢向溶液 A中 加入 84g浓度为 30wt%的双氧水后, 保温反应 2h; 反应结束后, 所得溶液经 300 mL饱和亚硫酸钠溶液洗涤、 减压蒸除乙酸甲酯和丙酸甲酯后, 得到 2,2’-二硫乙 二酸。
[0113] 按质量计, 在温度为 22°C和搅拌条件下, 将 100g 2,2’-二硫乙二酸和 150g三氟乙 酸酐混合并保温 2h; 所得溶液减压蒸除过量三氟乙酸酐与生成的三氟乙酸后, 得到 2,2’-二硫乙二酸酐。
[0114] 按质量计, 在温度为 50°C的条件下, 将 40g脂环族环氧化合物 (牌号: H71, 环 氧当量: 154g/eq) 和 60g缩水甘油酯型环氧树脂 (牌号: 672, 环氧当量: 161g/e q) 、 44g 2,2’-二硫乙二酸酐、 30g甲基六氢邻苯二甲酸酐和 0.5g 2 -乙基 -4 -甲基咪 唑混合均匀, 而后按照 80°C/2h+100°C/2h+120°C/2h+140°C/2h+160°C/4h的工艺进 行固化, 自然冷却后脱模, 得到一种可逆自修复环氧树脂。 [0115] 按质量计, 在温度为 50°C的条件下, 将 4g脂环族环氧化合物 (牌号: H71, 环 氧当量: 154g/eq) 和 6g缩水甘油酯型环氧树脂 (牌号: 672, 环氧当量: 161g/eq ) 、 4.4g 2,2’-二硫乙二酸酐、 3g甲基六氢邻苯二甲酸酐和 0.05g 2 -乙基 -4 -甲基咪 唑混合均匀, 得到预聚物 B ; 向预聚物 B中加入丙酸甲酯和丙酸乙酯和 1.72g未经 表面处理的单壁碳纳米管, 混合均匀, 涂布在步骤 (2) 制得的可逆自修复环氧 树脂上, 经挥发丙酸甲酯和丙酸乙酯, 按照 80°C/2h+100°C/2h+120°C/2h+140°C/2 h+160°C/4h的工艺进行固化, 自然冷却后, 得到一种电热环氧树脂复合材料, rg 超过 110°C。
[0116] 按质量计, 将 4g纳米铜粉与 0.8g全氟癸酸分散在水中, 混合均匀后静置、 过滤 , 水洗滤饼后烘干, 得到改性超疏水铜粉。
[0117] 按质量计, 在温度为 50°C的条件下, 将 4g脂环族环氧化合物 (牌号: H71, 环 氧当量: 154g/eq) 和 6g缩水甘油酯型环氧树脂 (牌号: 672, 环氧当量: 161g/eq ) 、 4.4g 2,2’-二硫乙二酸酐、 3g甲基六氢邻苯二甲酸酐和 0.05g 2 -乙基 -4 -甲基咪 唑混合均匀, 得到预聚物 C; 将预聚物 C涂布在步骤 (3) 制得的电热环氧树脂复 合材料上, 再将改性超疏水铜粉均匀分散在预聚物 C上, 而后按照 80°C/2h+100°C /2h+120°C/2h+140°C/2h+160°C/4h的工艺进行固化, 自然冷却后, 得到一种超疏 水电热环氧树脂复合材料, 水滴在电热环氧树脂复合材料的表面呈散开的半球 状, 表明超疏水电热环氧树脂复合材料具有类似于荷叶的良好超疏水性能。
[0118] 将复合材料与水平方向大约呈 3。放置, 两端施加 10V电压预热, 随后在其表面 放置少量碎冰, 经过 26秒, 碎冰可完全溶解并从复合材料表面自动滑落, 且无 液滴残留。 这一现象充分证明复合材料在超疏水表面与电热中间层的共同作用 下具有良好的除冰效果, 可用作风电叶片除冰防冰领域。
[0119] 超疏水电热环氧树脂复合材料的自修复方法
[0120] 将断裂的超疏水电热环氧树脂复合材料的断面处用夹具固定并紧密贴合, 在温 度为 185°C的条件下处理 1.5h, 断裂样品可重新连接在一起完成自修复且复合材 料在自修复后仍然保持了其良好的超疏水性能。
[0121] 实施例 8
[0122] 具体步骤如下: 按质量计, 在温度为 25°C的条件下, 将 120g 2 -巯基乙酸、 300g 乙酸乙酯和 300g丙酸乙酯及 l.Og碘化钾混合均匀, 形成溶液 A; 缓慢向溶液 A中 加入 85g浓度为 30wt%的双氧水后, 保温反应 2.5h; 反应结束后, 所得溶液经 300 mL饱和亚硫酸钠溶液洗涤、 减压蒸除乙酸乙酯和丙酸乙酯后, 得到 2,2’-二硫乙 二酸。
[0123] 按质量计, 在温度为 24°C和搅拌条件下, 将 100g 2,2’-二硫乙二酸和 135g三氟乙 酸酐混合并保温 2h; 所得溶液减压蒸除过量三氟乙酸酐与生成的三氟乙酸后, 得到 2,2’-二硫乙二酸酐。
[0124] 按质量计, 在温度为 50°C的条件下, 将 70g脂环族环氧化合物 (牌号: H71, 环 氧当量: 154g/eq) 和 30g缩水甘油醚型环氧树脂 (牌号: E51 , 环氧当量: 196g/ eq) 、 52g 2,2’-二硫乙二酸酐、 31g甲基六氢邻苯二甲酸酐和 0.5g 2 -乙基 -4 -甲基 咪唑混合均匀, 而后按照 80°C/2h+100°C/2h+120°C/2h+140°C/2h+160°C/4h的工艺 进行固化, 自然冷却后脱模, 得到一种可逆自修复环氧树脂。
[0125] 按质量计, 在温度为 50°C的条件下, 将 7g脂环族环氧化合物 (牌号: H71, 环 氧当量: 154g/eq) 和 3g缩水甘油醚型环氧树脂 (牌号: E51 , 环氧当量: 196g/e q) 、 5.2g 2,2’-二硫乙二酸酐、 3.1g甲基六氢邻苯二甲酸酐和 0.05g 2 -乙基 -4 -甲基 咪唑混合均匀, 得到预聚物 B ; 向预聚物 B中加入乙酸甲酯和 2.84g未经表面处理 的多壁碳纳米管, 混合均匀, 涂布在步骤 (2) 制得的可逆自修复环氧树脂上, 经挥发乙酸甲酯, 按照 80°C/2h+100°C/2h+120°C/2h+140°C/2h+160°C/4h的工艺进 行固化, 自然冷却后, 得到一种电热环氧树脂复合材料, rg超过 iio°c
[0126] 按质量计, 将 4g纳米铜粉与 0.8g全氟癸酸分散在水中, 混合均匀后静置、 过滤 , 水洗滤饼后烘干, 得到改性超疏水铜粉。
[0127] 按质量计, 在温度为 50°C的条件下, 将 7g脂环族环氧化合物 (牌号: H71, 环 氧当量: 154g/eq) 和 3g缩水甘油醚型环氧树脂 (E51, 环氧当量: 196g/eq) 、 5. 2g 2,2’-二硫乙二酸酐、 3.1g甲基六氢邻苯二甲酸酐和 0.05g 2 -乙基 -4 -甲基咪唑混 合均匀, 得到预聚物 C; 将预聚物 C涂布在步骤 (3) 制得的电热环氧树脂复合材 料上, 再将改性超疏水铜粉均匀分散在预聚物 C上, 而后按照 80°C/2h+100°C/2h+ 120°C/2h+140°C/2h+160°C/4h的工艺进行固化, 自然冷却后, 得到一种超疏水电 热环氧树脂复合材料, 水滴在电热环氧树脂复合材料表面呈散开的半球状, 表 明超疏水电热环氧树脂复合材料具有类似于荷叶的良好超疏水性能。
[0128] 将复合材料与水平方向大约呈 3。放置, 两端施加 10V电压预热, 随后在其表面 放置少量碎冰, 经过 26秒, 碎冰可完全溶解并从复合材料表面自动滑落, 且无 液滴残留。 这一现象充分证明复合材料在超疏水表面与电热中间层的共同作用 下具有良好的除冰效果, 可用作风电叶片除冰防冰领域。
[0129] 超疏水电热环氧树脂复合材料的自修复方法
[0130] 将断裂的超疏水电热环氧树脂复合材料的断面处用夹具固定并紧密贴合, 在温 度为 175°C的条件下处理 1.3h, 断裂样品可重新连接在一起完成自修复且复合材 料在自修复后仍然保持了其良好的超疏水性能。
[0131] 实施例 9超疏水电热环氧树脂复合材料的自修复
[0132] 将断裂的超疏水电热环氧树脂复合材料 (实施例 1制备) 的断面用夹具固定并 紧密贴合, 在温度为 160°C的条件下处理 lh; 其自修复效果数码照片和自修复后 的静接触角测试数码照片分别见附图 11和 12。
[0133] 参见附图 11, 它是本发明实施例 1制备的超疏水电热环氧树脂复合材料的自修 复效果数码照片。 将原始的复合材料从中间切断作为断裂样品, 随后用夹具固 定断裂样品两端置于 160°C的鼓风烘箱中加热 lh, 通过可逆二硫醚键的交换反应 , 断裂样品可重新连接在一起完成自修复, 仅在其表面留下一道类似于人类皮 肤在伤口愈合后的疤痕。
[0134] 参见附图 12, 它是本发明实施例 1制备的超疏水电热环氧树脂复合材料自修复 后的静接触角测试数码照片。 水滴在修复后的超疏水电热环氧树脂复合材料表 面的形态仍然可保持为近似圆球状 (图 12a) , 尤其是在自修复后残留的疤痕处 , 水滴形态与其他部分保持一致。 与原始的复合材料相比, 自修复后表面的静 态接触角为 152.0。 (图 12b) , 说明复合材料在自修复后仍然保持了其良好的超 疏水性能。
[0135] 本发明将 2,2’-二硫乙二酸酐与甲基六氢邻苯二甲酸酐按比例混合, 加入环氧树 月旨, 固化, 得到可逆自修复环氧树脂, 在该树脂上均匀涂布碳纳米管 /环氧树脂 预聚物, 固化, 即得到电热环氧树脂基复合材料; 在该复合材料表面均匀粘附 改性超疏水铜粉, 而后固化, 即得到一种超疏水电热环氧树脂复合材料。 本发 明利用可逆二硫醚键的交换反应, 同时实现环氧树脂、 电热层和超疏水层的快 速自修复。 本发明提供的电热环氧树脂复合材料对开裂剥离等重大损伤具有可 逆自修复的同时, 耐热性十分突出, 超过现有高分子基可逆自修复电热涂层。 本发明提供的超疏水电热环氧树脂复合材料可有效修复开裂、 剥离等重大损伤 , 而且修复后仍具有良好的超疏水效果。 本发明提供的超疏水电热环氧树脂复 合材料在满足风电叶片防冰除冰技术要求的同时, 具有额外的可逆自修复性能 , 可有效保障风电机组的运行安全并延长使用寿命。

Claims

权利要求书 [权利要求 1] 一种超疏水电热环氧树脂复合材料的制备方法, 其特征在于, 包括如 下步骤: ( 1) 按质量计, 在温度为 50〜 70°C的条件下, 将 100份环氧树脂、 42 〜 84份 2,2’-二硫乙二酸酐、 0〜 43份甲基六氢邻苯二甲酸酐混合均匀, 经固化后, 得到可逆自修复环氧树脂; (2) 按质量计, 在温度为 50〜 70°C的条件下, 将 10份环氧树脂、 4.2 〜 8.4份 2,2’-二硫乙二酸酐和 0〜 4.3份甲基六氢邻苯二甲酸酐混合均匀 , 得到预聚物; 向预聚物中加入酯溶剂和 0.1〜 4份碳纳米管, 混合均 匀得到涂布物; 然后将涂布物涂布在步骤 ( 1) 制得的可逆自修复环 氧树脂上, 经挥发酯溶剂、 固化后, 得到电热环氧树脂复合材料;(3) 按质量计, 将 4份纳米铜粉与 0.1〜 2份全氟羧酸分散在水中, 混 合均匀后静置、 过滤、 干燥, 得到改性超疏水铜粉; (4) 按质量计, 在温度为 50〜 70°C的条件下, 将 10份环氧树脂、 4.2 〜 8.4份 2,2’-二硫乙二酸酐、 0〜 4.3份甲基六氢邻苯二甲酸酐混合均匀 , 得到混合物; 将混合物、 改性超疏水铜粉依次设置在步骤 (2) 制 得的电热环氧树脂复合材料上, 固化后, 得到超疏水电热环氧树脂复 合材料。 [权利要求 2] 根据权利要求 1所述超疏水电热环氧树脂复合材料的制备方法, 其特 征在于, 所述 2,2’ -二硫乙二酸酐的制备方法如下:
( 1) 按质量计, 在温度为 20〜 30°C的条件下, 将 120份 2 -巯基乙酸、 500〜 700份酯类溶剂和 0.6〜 1.2份碘化钾混合均匀, 形成溶液; 缓慢 向溶液中加入 80〜 90份浓度为 30wt%的双氧水后, 保温反应 2〜 4h, 得到 2,2’-二硫乙二酸;
(2) 按质量计, 在温度为 20〜 30°C和搅拌条件下, 将 100份 2,2’-二硫 乙二酸和 120〜 150份酸酐混合并保温反应 2〜 4h, 得到 2,2’-二硫乙二 酸酐。
[权利要求 3] 一种电热环氧树脂复合材料的制备方法, 其特征在于, 包括如下步骤 ( 1) 按质量计, 在温度为 50〜 70°C的条件下, 将 100份环氧树脂、 42 〜 84份 2,2’-二硫乙二酸酐、 0〜 43份甲基六氢邻苯二甲酸酐混合均匀
, 经固化后, 得到可逆自修复环氧树脂;
(2) 按质量计, 在温度为 50〜 70°C的条件下, 将 10份环氧树脂、 4.2 〜 8.4份 2,2’-二硫乙二酸酐和 0〜 4.3份甲基六氢邻苯二甲酸酐混合均匀 , 得到预聚物; 向预聚物中加入酯溶剂和 0.1〜 4份碳纳米管, 混合均 匀得到涂布物; 然后将涂布物涂布在步骤 ( 1) 制得的可逆自修复环 氧树脂上, 经挥发酯溶剂、 固化后, 得到电热环氧树脂复合材料。
[权利要求 4] 根据权利要求 1、 2或者 3所述的制备方法, 其特征在于: 所述酯溶剂
、 酯类溶剂独立的选自乙酸甲酯、 乙酸乙酯、 乙酸丙酯、 丙酸甲酯、 丙酸乙酯的一种或几种。
[权利要求 5] 根据权利要求 1所述的制备方法, 其特征在于: 所述全氟羧酸为全氟 辛酸、 全氟壬酸、 全氟癸酸中的一种或几种。
[权利要求 6] 根据权利要求 1或者 3所述的制备方法, 其特征在于: 所述环氧树脂为 缩水甘油醚型环氧树脂、 缩水甘油酯型环氧树脂、 缩水甘油胺型环氧 树脂、 脂肪族环氧化合物、 脂环族环氧化合物中的一种, 或它们的任 意组合; 所述碳纳米管为未经表面处理的单壁碳纳米管、 多壁碳纳米 管中的一种, 或它们的任意组合。
[权利要求 7] 根据权利要求 2所述的一种可逆自修复环氧树脂的制备方法, 其特征 在于: 所述酸酐为乙酸酐、 三氟乙酸酐中的一种, 或它们的任意组合
[权利要求 8] 权利要求 1所述超疏水电热环氧树脂复合材料的制备方法制备的超疏 水电热环氧树脂复合材料; 或者权利要求 3所述电热环氧树脂复合材 料的制备方法制备的电热环氧树脂复合材料。
[权利要求 9] 权利要求 8所述超疏水电热环氧树脂复合材料的自修复方法, 其特征 在于, 包括以下步骤, 将受损超疏水电热环氧树脂复合材料的断面用 夹具固定并紧密贴合, 在温度为 160〜 200°C的条件下处理 1〜 3小时, 完成超疏水电热环氧树脂复合材料的自修复。
[权利要求 10] 权利要求 8所述电热环氧树脂复合材料的自修复方法, 其特征在于, 包括以下步骤, 将受损电热环氧树脂复合材料的断面用夹具固定并紧 密贴合, 在温度为 160〜 200°C的条件下处理 1〜 3小时, 完成电热环氧 树脂复合材料的自修复。
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