CN106085263B - A kind of light curing resin composition quickly repaired for aircraft non-bearing covering - Google Patents
A kind of light curing resin composition quickly repaired for aircraft non-bearing covering Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
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Abstract
This application discloses a kind of light curing resin composition quickly repaired for aircraft non-bearing covering, it includes：Photosensitive prepolymer acrylic modified epoxy resin prepolymer or the weight portion of polyurethane modified epoxy resin prepolymer 65 85, the weight portion of photoinitiator 26, the weight portion of photosensitive diluent 10 15, photocured cross-linked dose of 46 weight portions, the weight portion of silane coupler 0.3 0.6.The present invention can quickly repair the broken hole at aircraft non-bearing position, and aircraft skin operation repairing is completed in a short time, and with sufficient adhesive strength.
Description
Technical Field
The invention relates to a light-cured resin composition for quickly repairing non-bearing skin of an airplane.
Background
A quick repairing technology for the patch of photo-cured composite material features that the flexible prepreg repairing patch is made up of the reinforcing fibre material impregnated with photosensitive resin and then adhered to the damaged area by adhesion, and is quickly cured under the irradiation of ultraviolet light. The ultraviolet curing technology is applied to the field of emergency repair of aviation equipment, is suitable for rapid emergency repair of various damage forms and complex structural parts, and has strong universality and convenient and rapid operation. Due to the long storage period of the repair patch, the repair patch can be prepared in advance as a wartime reserve so as to reduce the dependence on spare parts. The first-aid repair equipment has small volume, light weight and convenient carrying, and is suitable for field operation.
The light cured prepreg adhering repair technology is a method for quickly repairing the damage forms of cracks, holes, corrosion, burns and the like by using the characteristic of high curing speed of photosensitive adhesive, using the photosensitive adhesive as matrix resin and using fibers as reinforcing materials to prepare a prepreg repair patch, selecting a proper repair patch according to the requirement of a repair object and quickly curing the repair patch under the irradiation of ultraviolet light, and the method has the technical characteristics that:
(1) rapidity: the repair process is simple, the operation is convenient, and the time from preparation and repair to equipment use is short;
(2) reliability: screws or rivets are not used for repairing, drilling is not needed, a new stress concentration source cannot be formed after repairing, the bearing area is large, and the repairing strength is high;
(3) easy forming: the repair patch is flexible before curing, can be randomly changed in shape according to requirements when being pasted, and is suitable for repairing the damage of various parts with complex shapes;
(4) the accessibility is good: the bonding repair uses few tools, can be operated in a small working space, and is also suitable for repairing the internal damage of the machine body with a narrow space;
(5) self-forming system: needs few external resources, uses few tools and equipment in operation, and is convenient for emergency repair in the field;
(6) the universality is good: the method is suitable for repairing materials such as metal, composite materials and the like;
(7) the weight gain is less: the adhesive repairing patch belongs to a high molecular organic material, has light weight, and saves metal connecting pieces such as screws, rivets and the like, so the weight is increased little after repairing.
The airplane body mode mainly comprises several modes of replacing parts, riveting, welding, temporarily reinforcing and the like, and the traditional first-aid repair methods generally have the defects of complex process, long time, more equipment and the like. The rapid repair technology of the light-cured composite material patch needs less equipment, short time and simple process, and is particularly suitable for civil aircrafts. The application of the technology has better economic benefit for improving the capability of roading without rush repair to the operation of the airplane.
At present, the rapid repair technology of the photo-curing composite material patch is researched and applied at home and abroad, and the literature introduces the photosensitive resin adhesive patch bonding technology used by the army and the American Boeing company to repair the airplane damage. The air and navy of our army has a unit research technology, and the air force hospital also carries out a deeper thermosetting adhesive research test (the pressure of 49-73 kPa is loaded, the pressure is removed after 10 hours of pressure curing, and the pressure curing temperature is 18-35 ℃).
The inventor reports a photocuring composite material and application thereof in repairing various structural damages of airplanes in 'bonding application research of modified epoxy resin photocuring quick-adhesion glue' published in 'Chinese adhesive', and adopted test raw materials comprise acrylic acid modified epoxy resin photosensitive prepolymer, Dymax series UV curing adhesive, butyl acrylate, acetone, 95% ethanol, acetic acid, triethylene glycol diacrylate, photoinitiator, silane coupling agent and the like.
Disclosure of Invention
The invention is made in view of the problems, and aims to provide a light-cured resin composition for quickly repairing non-bearing skin of an airplane.
The photocurable resin composition of the present invention comprises:
the photocurable resin composition of the present invention preferably further comprises:
0.05 to 0.25 part by weight of corrosion inhibitor.
The photosensitive prepolymer, the acrylic modified epoxy prepolymer, preferably has a number average molecular weight of 400-1500 daltons.
The photosensitive prepolymer acrylic modified epoxy resin prepolymer is preferably synthesized by reacting a combination of both liquid epoxy resins E-51 and E-44, or a combination of both liquid epoxy resins E-54 and E-44 with acrylic acid or alpha-methacrylic acid under heating. The viscosity of the modified acrylic modified epoxy resin prepolymer is preferably 15 to 25 Pa.s. The weight ratio of the liquid epoxy resin E-51 to the liquid epoxy resin E-44 is 1-3:1-3, and the weight ratio of the liquid epoxy resin E-54 to the liquid epoxy resin E-44 is 1-3: 1-3.
These three epoxy resins are available, for example, from epoxy factories of the ba ling petrochemical company. E-51, viscosity, 10-15Pa.s, epoxy value 0.48-0.53; e-54, viscosity, 6-8Pa.s, epoxy value 0.55-0.56; e-44, viscosity, 12-20Pa.s, epoxy value 0.43-0.46; the mixing ratio of the two components can be 1: 3-3: 1 (mass ratio). As the reaction catalyst, tertiary amines such as trimethylamine or triethylamine can be used in an amount of 0.6 to 1.0 wt% based on the epoxy resin. It is also possible to prevent the acrylic acid from polymerizing itself during the reaction with a polymerization inhibitor such as hydroquinone, added in an amount of 0.10 to 0.15% by weight based on the amount of acrylic acid. As the reaction system has a large viscosity, toluene, xylene or the like is preferably used as a reaction solvent in an amount of 30 to 50 vol/wt% based on the total amount of the epoxy resin. After the reaction, the reaction system was cooled, and the solvent was removed by distillation under reduced pressure.
The polyurethane-modified epoxy resin prepolymer preferably has a number average molecular weight of 200 and 1200 daltons.
The polyurethane-modified epoxy prepolymer is preferably prepared by reacting a polyether diol with a diisocyanate using the aforementioned E-51 or E-54 (liquid) epoxy resin binder to prepare a polyether urethane (intermediate 1); intermediate 1 is then reacted with E-51 or E-54 or a mixture of E-51 and/or E54 and E-44 (E-51 and/or E54: E-44 ═ 1-3:1-3) to give a urethane-modified epoxy resin (intermediate 2); (intermediate 2) finally reacted with hydroxyalkyl acrylate to form the corresponding "urethane-modified epoxy (acrylate) prepolymer". The viscosity of the urethane-modified epoxy resin (acrylate) prepolymer is preferably 13 to 22 pa.s.
The photosensitive diluent is preferably one or more selected from hexyl acrylate, butyl methacrylate and isobornyl acrylate, and is more preferably a mixture of hexyl acrylate and butyl methacrylate in a volume ratio of 0.5-1.5: 0.5-1.5, and the mixture can obtain better bonding strength.
The silane coupling agent is preferably selected from the group consisting of vinyltriethoxysilane, vinyltrimethoxy, gamma-aminopropyltriethoxysilane, propenyl-triethoxysilane and vinyltriacetoxysilane.
The photoinitiator is preferably Irgacure184 (Ciba-Gaigey, Switzerland) and/or the photoinitiator Darocure 1173 (Ciba-Gaigey, Switzerland).
The corrosion inhibitor is preferably selected from the group consisting of fluoroorganics "Zonyl" series products from DuPont, USA, preferably Zonyl FSG.
Preferably, the photocurable resin composition of the present invention comprises:
the photocurable resin composition of the present invention preferably further comprises:
0.08-0.12 part of corrosion inhibitor.
The corrosion inhibitor is preferably selected from the group consisting of fluoroorganics "Zonyl" series products from DuPont, USA, preferably Zonyl FSG, or 0.2 wt% S217 is used.
The photocurable crosslinking agent is preferably selected from the group consisting of triethylene glycol diacrylate (TEGDA), tetraethylene glycol diacrylate (TTGDA), diethylene glycol diacrylate (DEGDA).
The method for preparing the photocurable resin composition of the present invention comprises uniformly mixing the above-mentioned various components.
The invention further provides a method for rapidly repairing non-bearing skin of an airplane by using the composition, which comprises the steps of impregnating fiber reinforced materials (preferably high-strength glass fibers such as glass fiber cloth) to prepare a flexible prepreg repairing patch, adhering the flexible prepreg repairing patch to a damage area by using a bonding method, and rapidly curing the flexible prepreg repairing patch under the irradiation of ultraviolet light.
The high-strength glass fiber includes: 1) the alkali-free Glass Fiber (E-Glass Fiber) mainly contains aluminoborosilicate, and has the advantages of good Electrical insulation, water resistance and mechanical strength, wherein the content of alkali metal oxide is 0-2%. The material is mainly used as an electric insulating material and a reinforcing material such as glass fiber reinforced plastic, engineering material, rubber and the like. 2) The medium alkali Glass Fiber (C-Glass Fiber) contains about 8-12% of alkali metal oxide, mainly contains calcium sodium silicate, has good acid resistance, has mechanical strength about 75% of that of alkali-free Glass Fiber, is mainly used as a base material of latex cloth and window screening, and also can be used as acidic filter cloth and a reinforcing material with low requirements on electrical property and strength. In addition, it is less costly than alkali glass fibers. 3) High Alkali Glass Fiber (A-Glass Fiber), in which the content of Alkali metal oxide is about 14-17%, mainly contains calcium sodium silicate component. Its alkali content is high, so that it has poor mechanical strength, poor water-proofing property and good acid-proofing property. The raw materials are convenient to obtain, the cost is low, and the fabric can be used as a storage battery separator, a pipeline binding cloth, an asphalt felt base cloth and the like. 4) Special glass fiber, fiber with chemical composition suitable for special purpose, such as high elastic modulus glass fiber (M-glass fiber), introduced BeO and Li2O、ZrO2、TiO2(ii) a Radiation-proof glass fiber with PbO and ZrO introduced2、Ta2O3、WO3And the like.
THE ADVANTAGES OF THE PRESENT INVENTION
The method can quickly repair the broken hole at the non-bearing part of the airplane, complete the operation and the rush repair of the airplane skin in a short time, and has sufficient bonding strength.
Detailed Description
The present invention is illustrated by the following specific examples.
Synthesis example 1
In a (clean) 500ml three-necked flask equipped with a thermometer, a motor stirrer and a reflux condenser, 70ml of toluene was charged, 90g E-51 and 60g E-44 were added, and the mixture was dissolved completely with stirring (about 10-15min for stirring). 0.1g of hydroquinone and 1.2g of triethylamine were added. Heating to 75-80 deg.C and maintaining constant temperature, and starting to add 65g of acrylic acid dropwise, and adding about 35-40 drops per minute. After the dropwise addition, the temperature is raised to 105 ℃ and 110 ℃, and the reaction is continued for 2 h. After the reaction, the reaction product is cooled to 40-50 ℃, the reaction device is changed into a reduced pressure distillation device, and the solvent is removed by reduced pressure distillation under the vacuum degree of about 50-100 Pa. (Note: the degree of vacuum of the vacuum distillation is not particularly limited, and the lower the degree of vacuum, the lower the temperature required for heating the distillation). The residue after the solvent removal was the acrylic modified epoxy prepolymer, which had a viscosity of about 18.5 pa.s.
Synthesis example 2
E-54 instead of E-51 in example 1(90g E-55 and 60g E-44 instead of 90g E-51 and 60gE-44 in example 1), 70g of a-methacrylic acid instead of 65g of acrylic acid therein; other reaction conditions and reduced pressure distillation conditions are the same, and the alpha-methacrylic acid modified epoxy resin prepolymer is prepared. The prepared light curing adhesive is bonded with the impregnated glass fiber cloth and the duralumin alloy, and the bonding strength can reach 17.5 MPa.
Comparative Synthesis example 1
The same as in Synthesis example 1 except that 150g E-51 was used alone.
Comparative Synthesis example 2
The same as in Synthesis example 1 except that 150g E-54 was used alone.
Comparative Synthesis example 3
As in Synthesis example 1, except that 150g of E-44 was used alone.
Synthesis example 3
80g of a polyether diol (N204, molecular weight 400, hydroxyl number 270-. Heating to 80 ℃, and keeping the constant temperature of 80-85 ℃ for 2-2.5h to obtain the polyether polyurethane. Cooled to below 40 ℃, 25g dimethylolpropionic acid and 60g E-51 were added, and the viscosity was adjusted with an appropriate amount of acetone. Heating to above 65 deg.C, and reacting at 65-70 deg.C for 1 h. Cooling to 50 deg.C, adding 0.015g hydroquinone and 0.2g DBT, heating to above 60 deg.C, adding 32g hydroxypropyl acrylate dropwise (after about half an hour), and reacting at 65-70 deg.C for 2 h. Cooling to below 40 ℃ and discharging to obtain the polyurethane modified epoxy resin (acrylate) prepolymer. Viscosity 16.2 pa.s.
Synthesis example 4
A composition of E-51 and E-44 was used in place of E-51 in Synthesis example 3.
Synthesis example 5
Dipropylene glycol 30g was used instead of 80g of the polyether glycol in synthetic example 3.
Synthesis example 6: synthesis of urethane acrylate resin prepolymer
100g of polyethylene glycol 200 (molecular weight 200, commercially available) were placed in a 500ml three-necked flask equipped with a thermometer, an electric stirrer and a reflux condenser, and 65ml of TDI (toluene diisocyanate), 0.35g of DBT (dibutyltin dilaurate) and 0.25g of stannous octoate were added with stirring. Heating to 80 ℃, and keeping the constant temperature of 80-85 ℃ for 2-3h to obtain the polyether polyurethane. Cooling to below 50 deg.C, adding 0.05g hydroquinone, heating to 55 deg.C, adding 50g hydroxypropyl acrylate dropwise (after about 40 min), and reacting at 55-60 deg.C for 2 hr. Cooling to 40 ℃ and discharging to obtain the urethane acrylate resin prepolymer.
Comparative Synthesis example 4
The same as in Synthesis example 3 except that E-44 was used in place of E-51.
Example 1
The components are uniformly mixed to prepare the light-cured resin adhesive. The prepared light curing adhesive is used for impregnating glass fiber cloth and bonding hard aluminum alloy, and the bonding strength can reach 18.5 MPa.
Example 2
The same as in example 1 except that the acrylic-modified epoxy resin prepolymer of Synthesis example 2 was used. The prepared light curing adhesive is bonded with the impregnated glass fiber cloth and the duralumin alloy, and the bonding strength reaches 17.5 MPa.
Comparative example 1
As in example 1, except that the acrylic modified epoxy resin prepolymer of comparative Synthesis example 1 was used, the adhesive prepolymer obtained was low in adhesive strength, and adhered to a duralumin alloy with an adhesive strength of only 16.5 MPa.
Comparative example 2
As in example 1, except for using the acrylic modified epoxy resin prepolymer of comparative Synthesis example 2, the adhesive prepolymer obtained was low in adhesive strength, and adhered to a duralumin alloy with an adhesive strength of only 16.2 MPa.
Comparative example 3
As in example 1, except for using the acrylic modified epoxy resin prepolymer of comparative Synthesis example 3, the resulting photocurable resin adhesive E-44 was poor in leveling property and could not be uniformly coated.
Example 3
The components are uniformly mixed to prepare the light-cured resin adhesive.
Compared with the epoxy acrylate prepolymer in the embodiment 1 and the embodiment 2, the polyurethane modified epoxy resin (acrylate) prepolymer in the embodiment has better corrosion resistance, good polymer chain flexibility of the photo-cured adhesive, and small volume shrinkage of the photo-cured adhesive. However, the bonding strength (bonding duralumin alloy) of the light-cured adhesive is slightly lower than that of the light-cured adhesive prepared from epoxy acrylate prepolymer, and is about 16.5 MPa. However, compared with epoxy acrylate prepolymer, the corrosion time caused by soaking in 5 wt% NaCl solution is prolonged by more than 5-6h to about 8-10 h.
Example 4
Similar to example 3, except that the urethane-modified epoxy resin of Synthesis example 4 was used in place of the urethane-modified epoxy resin of Synthesis example 3, the bonding strength of the prepared photo-curable adhesive was about 2MPa lower and 16.5MPa lower than that of the photo-curable adhesive prepared from the epoxy acrylate prepolymer (synthesized from the composition of E-51 and E-44) of Synthesis example 1, but as described above, the urethane-modified epoxy resin (acrylate) prepolymer of this example had better corrosion resistance, good flexibility of the polymer chain of the photo-curable adhesive, and the volume shrinkage of the adhesive after photo-curing was small. Compared with epoxy acrylate prepolymer, the corrosion time caused by soaking in 5 wt% NaCl solution is prolonged by more than 5-6 h.
Example 5
The same as in example 3 except that the urethane-modified epoxy resin of Synthesis example 5 was used. The formulated light-curable glue was compared to the prepolymer of synthesis example 3: the high molecular chain flexibility of the light-cured adhesive is slightly low, and the bonding strength is about 1MPa and reaches about 17.5 MPa.
Example 6
Similarly to example 3, 37.5 parts by weight of the prepolymer of Synthesis example 6 and 37.5 parts by weight of the prepolymer of Synthesis example 1 were mixed in a mass ratio of 1:1 in place of 75 parts by weight of the urethane-modified epoxy resin of Synthesis example 3 to prepare a photocurable adhesive. Compared with the light-cured adhesive prepared by the prepolymer in the synthesis example 1, the adhesive strength is lower by about 1MPa and about 17.5MPa, but the corrosion time caused by soaking in a 5 wt% NaCl aqueous solution is prolonged by more than 4-5 h.
Comparative example 4
Similar to example 3, except that the urethane-modified epoxy resin of comparative synthesis example 4 was used in place of the urethane-modified epoxy resin of synthesis example 3. As a result, the hard aluminum alloy was bonded with a bonding strength of about 15.5 MPa.
Testing of high and Low temperature resistance
1) And (3) high temperature resistance test, namely placing dozens of pieces of adhesive piece samples in a constant temperature drying oven with the temperature of 80 +/-1 ℃ and the temperature of 100 +/-1 ℃, baking for 8, 12, 16, 20, 24 and 48 hours, taking out 5 pieces of adhesive piece samples each time, and measuring the change of lap shear strength. Since the polymer bond strength decreases exponentially with increasing temperature, it is expected that if the bond is baked at 100 + -1 deg.C for 24 or more and the bond strength decreases within 20%, or baked at 80 + -1 deg.C for 48 or more and the bond strength decreases within 20%, the bond will be able to withstand desert temperatures of 50 to 60 deg.C for at least 1 month to 45 days, according to previous bond studies in other application areas.
2) And (3) low temperature resistance test, wherein dozens of pieces of adhesive piece samples are respectively placed in a refrigerator at the temperature of-20 +/-1 ℃ and a freezing circulation tank at the temperature of-40 +/-1 ℃, and are frozen for 24, 48 and 72 hours until 168 hours, and then 5 pieces are taken out each time to measure the change of lap shear strength.
Two high temperature conditions of 60 ℃ and 100 ℃ and two low temperature conditions of-18 ℃ and-40 ℃ are respectively set. The results of the bond strength change of the bond of example 1 after a period of sustained standing at 60 ℃ are shown in table 2; the results of the bond strength change of the bonds of example 4 after a period of constant standing at 60 c are shown in table 3. The results of the change in the adhesive strength after a prolonged standing period at 100 ℃ are shown in Table 4; the results of the test for the change in the shear strength after a prolonged standing at-18 ℃ are shown in Table 5; the results of the test for the change in the shear strength after a prolonged standing at-40 ℃ are shown in Table 6.
Table 2 results of change in adhesive strength of the adhesive of example 1 after standing at 60 c for a period of time (adhesion of 2 glass fiber cloth)
| Temperature (. degree.C.) | Standing time (h) | Maximum force (Fm) | Area of tension crack (cm)2) | Tensile Strength (MPa) |
| 60 | 8 | 2983.5 | 1.9 | 15.7 |
| 60 | 16 | 3588.1 | 2.3 | 15.6 |
| 60 | 24 | 3260.4 | 2.0 | 16.3 |
| 60 | 32 | 2431.7 | 1.5 | 16.2 |
| 60 | 40 | 2686.3 | 1.7 | 15.8 |
| 60 | 48 | 4651.0 | 3.0 | 15.5 |
Table 3 results of change in adhesive strength of the adhesive of example 4 after standing at 60 c for a period of time (bonding 2 glass fiber cloth)
| Temperature (. degree.C.) | Standing time (h) | Maximum force (Fm) | Area of tension crack (cm)2) | Tensile Strength (MPa) |
| 60 | 8 | 4312.9 | 2.8 | 15.4 |
| 60 | 16 | 3046.5 | 2.1 | 14.5 |
| 60 | 24 | 1797.6 | 1.2 | 14.8 |
| 60 | 32 | 7753.2 | 5.1 | 15.2 |
| 60 | 40 | 5441.0 | 3.4 | 16.0 |
| 60 | 48 | 3589.7 | 2.3 | 15.6 |
TABLE 4 results of change in adhesive strength after standing at 100 ℃ for a certain period of time (adhesion of 2 layers of glass fiber cloth)
TABLE 5-18 ℃ Change in bond Strength after standing (bonding of 2 layers of glass fiber cloth)
TABLE 6 results of measurement of change in shear strength of adhesive bond after continuous standing at 40 ℃ (adhesion of 2-ply glass fiber cloth)
As can be seen from tables 2 and 3, the photocurable adhesive materials of examples 1 and 4 hardly cause a significant decrease in adhesive strength when left at 60 ℃ for 48 hours or more; the change in bond strength caused by a continuous 48h exposure at-18 ℃ was also small, up to 72h, with only a 10% reduction in the shear strength of the example 1 bond, and almost no reduction in the shear strength of the example 4 bond (see table 5). As can be seen from table 4, the adhesive of example 1 had a very small (2%) decrease in shear strength even when left at an extremely high temperature of 100 ℃ for 12h, and the adhesive of example 4 had a decrease in shear strength of about 10%; while the adhesive of example 1 showed little (3%) decrease in shear strength after 72h at an extremely low temperature of-40 c, the adhesive of example 4 showed little change in shear strength (see table 6). The adhesive of example 1 was more excellent in high temperature resistance, while the adhesive of example 4 was particularly excellent in low temperature resistance.
Examples 1 and 4 were able to smoothly cure the photo-curable adhesive not only at 100 ℃ but also at a low temperature of-40 ℃.
High speed wind tunnel test
In order to further investigate the phenomenon that the high-speed airflow impact caused by a propeller resistance of the light curing adhesive patch can cause the damage of an adhesive layer under the normal flight condition, and on the other hand, to investigate whether the patch has adverse effect on the flow of the airflow in flight, a wind tunnel test is carried out, and the test method refers to the standard: GJB (national military standard) 4008-. After the bonding piece samples of the three-layer glass fiber cloth and the duralumin alloy bonded by the compositions in the embodiment 1 and the embodiment 3 are subjected to continuous air blowing of 0.8 Mach, 1.2 Mach and 1.5 Mach (900, 1300 and 1600km/h) crossing and supersonic speed wind tunnels for 24 hours, the phenomenon of peeling or loosening of the bonding part does not occur; furthermore, for the three sizes of 5cm X5 cm, 15cm X15 cm and 25cm X25cm patch, there was no effect on the normal flow of the airflow that could be detected by the instrument.
Claims (12)
1. A photocurable resin composition for rapid repair of non-stressed skins of an aircraft, the composition comprising:
65-85 parts by weight of photosensitive prepolymer acrylic modified epoxy resin prepolymer or polyurethane modified epoxy resin prepolymer,
2-6 parts by weight of a photoinitiator,
10-15 parts by weight of a photosensitive diluent,
4-6 parts of a photo-curing cross-linking agent,
0.3-0.6 part by weight of silane coupling agent;
the photosensitive prepolymer acrylic modified epoxy resin prepolymer is synthesized by reacting a composition of liquid epoxy resins E-51 and E-44, or a composition of liquid epoxy resins E-54 and E-44 with acrylic acid or alpha-methacrylic acid under heating; the weight ratio of the liquid epoxy resin E-51 to the liquid epoxy resin E-44 is 1-3:1-3, and the weight ratio of the liquid epoxy resin E-54 to the liquid epoxy resin E-44 is 1-3: 1-3;
or,
the polyurethane-modified epoxy resin prepolymer is a polyurethane-modified epoxy resin prepolymer obtained by: reacting polyether glycol with diisocyanate by using E-51 or E-54 liquid epoxy resin base material to prepare intermediate 1 polyether urethane; intermediate 1 is then reacted with E-51 or E-54, or with 1-3:1-3 to obtain an intermediate 2 polyurethane modified epoxy resin; and finally, the intermediate 2 reacts with hydroxyalkyl acrylate to generate corresponding polyurethane modified epoxy resin prepolymer.
2. The photocurable resin composition of claim 1, comprising:
75-80 parts by weight of photosensitive prepolymer acrylic modified epoxy resin prepolymer or polyurethane modified epoxy resin prepolymer,
3-4 parts by weight of a photoinitiator,
11-14 parts of a mixture of photosensitive diluent hexyl acrylate and butyl methacrylate with the volume ratio of 0.5-1.5: 0.5-1.5,
4.5 to 5 parts by weight of a photo-curing crosslinking agent,
silane coupling agent vinyl triethoxy silane and/or vinyl trimethoxy silane 0.4-0.5 weight parts.
3. The photocurable resin composition of claim 1, further comprising:
0.05 to 0.25 part by weight of corrosion inhibitor.
4. The photocurable resin composition of claim 2, further comprising:
0.08-0.12 part of corrosion inhibitor.
5. The photocurable resin composition according to any one of claims 1-4, wherein the photoinitiator is Irgacure184 or the photoinitiator Darocure 1173.
6. The photocurable resin composition according to claim 5, wherein the corrosion inhibitor is selected from the group consisting of Zonyl series products of fluorinated organic compounds from DuPont.
7. The photocurable resin composition of claim 6, wherein the corrosion inhibitor is selected from ZonylFSG from DuPont, USA.
8. The photocurable resin composition according to any one of claims 1-4, wherein the photocurable crosslinker is selected from the group consisting of triethylene glycol diacrylate (TEGDA), tetraethylene glycol diacrylate (TTGDA), and diethylene glycol diacrylate (DEGDA).
9. The photocurable resin composition according to claim 5, wherein the photocurable crosslinking agent is selected from the group consisting of triethylene glycol diacrylate (TEGDA), tetraethylene glycol diacrylate (TTGDA), and diethylene glycol diacrylate (DEGDA).
10. The photocurable resin composition according to claim 6, wherein the photocurable crosslinking agent is selected from the group consisting of triethylene glycol diacrylate (TEGDA), tetraethylene glycol diacrylate (TTGDA), and diethylene glycol diacrylate (DEGDA).
11. A method of preparing the photocurable resin composition of any one of claims 1-10, said method comprising homogeneously mixing the ingredients.
12. A method of using the photocurable resin composition according to any one of claims 1-10 for the rapid repair of non-stressed aircraft skins, which comprises impregnating a fibrous reinforcement material to form a flexible prepreg repair patch, adhesively bonding the repair patch to the damaged area, and rapidly curing the repair patch under the irradiation of ultraviolet light.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1405888A1 (en) * | 2001-05-16 | 2004-04-07 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
| CN1789363A (en) * | 2005-12-02 | 2006-06-21 | 西安瑞联近代电子材料有限责任公司 | Preparation method of ultraviolet cured adhesive for flat panel display |
| CN101798492A (en) * | 2010-02-22 | 2010-08-11 | 北京高盟新材料股份有限公司 | Preparation method of ultraviolet light curing composite binding agent |
| CN102079810A (en) * | 2010-12-15 | 2011-06-01 | 北京航空航天大学 | Synthesis and application of light-cured polyurethane-acrylic acid-epoxy resin adhesive |
| CN104212396A (en) * | 2014-09-10 | 2014-12-17 | 湖南柯盛新材料有限公司 | Photo-curable resin composition for repairing facing marble plank and preparation and using method of photo-curable resin composition |
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2016
- 2016-07-21 CN CN201610580161.1A patent/CN106085263B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1405888A1 (en) * | 2001-05-16 | 2004-04-07 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
| CN1789363A (en) * | 2005-12-02 | 2006-06-21 | 西安瑞联近代电子材料有限责任公司 | Preparation method of ultraviolet cured adhesive for flat panel display |
| CN101798492A (en) * | 2010-02-22 | 2010-08-11 | 北京高盟新材料股份有限公司 | Preparation method of ultraviolet light curing composite binding agent |
| CN102079810A (en) * | 2010-12-15 | 2011-06-01 | 北京航空航天大学 | Synthesis and application of light-cured polyurethane-acrylic acid-epoxy resin adhesive |
| CN104212396A (en) * | 2014-09-10 | 2014-12-17 | 湖南柯盛新材料有限公司 | Photo-curable resin composition for repairing facing marble plank and preparation and using method of photo-curable resin composition |
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| Title |
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| "改性环氧树脂光固化速粘胶的粘接应用研究";马晓旺等;《中国胶粘剂》;20120229;第19卷(第2期);第33页前言部分，试验原料1.1，第34页1.3.1 * |
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|---|---|
| CN106085263A (en) | 2016-11-09 |
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