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 PDF

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Publication number
CN106085263B
CN106085263B CN201610580161.1A CN201610580161A CN106085263B CN 106085263 B CN106085263 B CN 106085263B CN 201610580161 A CN201610580161 A CN 201610580161A CN 106085263 B CN106085263 B CN 106085263B
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light curing
resin composition
prepolymer
curing resin
modified epoxy
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CN106085263A (en
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胡伟
程新平
朱吉军
李辉
赵子龙
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AVIAT ACADEMY OF PLA
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AVIAT ACADEMY OF PLA
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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
    • 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
    • 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
    • C09J11/06—Non-macromolecular additives organic

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

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

A kind of light curing resin composition quickly repaired for aircraft non-bearing covering
Technical field
The present invention relates to a kind of light curing resin composition quickly repaired for aircraft non-bearing covering.
Background technology
Light curing compound material sticking patch fast repair technique, is made flexible pre- with photosensitive resin dipping fibre reinforced materials Leaching material repaired patch, destruction damage zone is subsidized with the method for bonding, is solidified rapidly under the irradiation of ultraviolet light, so as in short-term Interior completion aircraft skin operation repairing.UV-curing technology is applied to aircraft equipment repairing field, it is adaptable to various damages The rapid rush-repair of form, complex structural member, it is highly versatile, easy to operate.Because repaired patch storage period is long, can make in advance It is standby to be laid in as wartime, to reduce the dependence to spare part.It is rush repair equipment small volume, lightweight, easy to carry, it is suitable to field work Industry.
Photocuring prepreg Bonding Repair technology is exactly the characteristics of utilizing light-sensitive emulsion curing rate fast, and matrix is made with light-sensitive emulsion Resin, with fiber as reinforcing material, is made prepreg repaired patch, according to the demand for repairing object, from suitable repairing Sticking patch, solidifies rapidly under the irradiation of ultraviolet light, is carried out quickly with reaching equivalent damage form of being burnt to crackle, hole, burn into The method of reparation, the technical characterstic of the method is as follows：
(1) rapidity：Repairing technology is simple, easy to operate, from the time for preparing, implementation repairing is come into operation to equipment It is short；
(2) reliability：Repairing does not use screw or rivet, does not need drilling, and new stress raiser will not be formed after repairing And loaded area is big, intensity is repaired high；
(3) easily shaping：Repaired patch in flexibility, can arbitrarily change its shape as needed before curing during stickup, be applicable In the damage repair of various complicated shape parts；
(4) accessibility is good：Bonding repairing used tool is few, can be operated in small working space, is also applied for narrow space Internal body damage repair；
(5) establish one's own system：Little external resource is needed, the instrument used in operation, equipment are few, are easy to field to rush to repair；
(6) versatility is good：Suitable for the repairing of the materials such as metal and composite；
(7) increase weight few：Bonding repaired patch belongs to macromolecule organic material, and own wt is light, and screw, rivet etc. are eliminated again Weight increases few after metal connecting piece, thus repairing.
Airframe mode mainly changes that part, riveting, welding and temperature pier etc. are several, and these traditional emergency repair methods are general Store-through complex process, the time is long, equipment is more the shortcomings of.Light curing compound material sticking patch fast repair technique need equipment it is few, Time is short, process is simple, is particularly well-suited to aircarrier aircraft.To improving, road is capable not to rush to repair energy to aircraft operation for the application of the technology Power, with preferable economic benefit.
Current light curing compound material sticking patch fast repair technique at home and abroad has research and application, has document to introduce beautiful Aircraft damage is repaired with Boeing Co. using photosensitive resin glue sticking patch adhesive technology by army.My Jun Kong naval has unit to study More deep heat-curable glue development test (pressure of loading (49~73) kPa, pressurization also did in technique, boat institute of air force one Pressure is shed after solidification 10h, cure under pressure temperature is 18~35 DEG C).
The present inventor exists《Chinese adhesive》On deliver " modified epoxy photocuring speed viscose glue bonding application grind Study carefully " in report a kind of light curing compound material and its application that repairing is gone around in the various structures destructions of machine, the experiment of use is former Material includes acrylic modified epoxy resin photosensitive prepolymer, Dymax series UV cured adhesives, butyl acrylate, acetone, 95% Ethanol, acetic acid, triethylene glycolbismethyl-acrylate, photoinitiator, silane coupler etc., however, the technology is still present Weak point is further improved, and such as adhesive strength is insufficient, high temperature resistant cryogenic property cannot meet and is actually needed sometimes.
The content of the invention
Made the present invention be directed to above mentioned problem, quickly repaiied for aircraft non-bearing covering the purpose is to provide one kind Multiple light curing resin composition.
Light curing resin composition of the invention includes：
Light curing resin composition of the invention preferably further includes：
The weight portion of corrosion inhibiter 0.05~0.25.
Photosensitive prepolymer, acrylic modified epoxy resin prepolymer, the equal molecule of number preferably with 400-1500 dalton Amount.
The photosensitive prepolymer acrylic modified epoxy resin prepolymer is preferably through liquid epoxies E-51 and E- 44 combination things, or application liquid epoxies E-54 and E-44 combinations thing and acrylic acid or Alpha-Methyl third Olefin(e) acid is reacted and is synthesized under heating.Modified acrylic modified epoxy resin prepolymer viscosity is preferably 15- 25Pa.s.The weight ratio of liquid epoxies E-51 and E-44 is 1~3:The weight of 1~3, liquid epoxies E-54 and E-44 Than being 1~3:1~3.
These three epoxy resin are for example purchased from epoxy resin factory of Ba Ling petro-chemical corporations.E-51, viscosity, 10-15Pa.s, epoxy Value 0.48-0.53；E-54, viscosity, 6-8Pa.s, epoxide number 0.55-0.56；E-44, viscosity, 12-20Pa.s, epoxide number 0.43- 0.46；The mixed proportion of the two can be 1:3–3:1 (mass ratio).Catalysts can use tertiary amine, for example trimethylamine or Triethylamine, the consumption that catalyst amount is based on epoxy resin accounts for 0.6-1.0wt%.Polymerization inhibitor such as hydroquinones can also be used, Prevent acrylic acid from the polymerisation of itself occurring during reaction, it is 0.10- that polymerization inhibitor addition is based on acrylic acid amount 0.15wt%.Because reaction system viscosity is larger, preferably with toluene, dimethylbenzene etc. as reaction dissolvent, the amount of solvent is based on ring Oxygen tree fat total amount is 30-50vol/wt%.Reaction is finished, cooling reaction system, and vacuum distillation removes solvent.
The polyurethane modified epoxy resin prepolymer preferably number-average molecular weight with 200-1200 dalton.
The polyurethane modified epoxy resin prepolymer preferably passes through with foregoing E-51 or E-54 (liquid) epoxy resin-matrix Material, allows PTMEG and di-isocyanate reaction, prepares EU (intermediate 1)；Intermediate 1 then with E-51 or E- Mixture (the E-51 and/or E54 of 54 or E-51 and/or E54 and E-44:E-44=1-3:1-3) react, obtain polyurethane and change Property epoxy resin (intermediate 2)；(intermediate 2) finally reacts with acrylic acid hydroxy alkyl ester, corresponding " the polyurethane-modified ring of generation Oxygen tree fat (acrylate) prepolymer ".The viscosity of polyurethane modified epoxy resin (acrylate) prepolymer is preferably 13- 22Pa.s。
Photosensitive diluent is preferably selected from the one kind in Hexyl 2-propenoate, butyl methacrylate and iso-bornyl acrylate Or various, more preferably Hexyl 2-propenoate and butyl methacrylate volume ratio 0.5~1.5:0.5~1.5 mixture, this is mixed Compound is obtained in that more preferable adhesive strength.
Silane coupler is preferably selected from VTES, vinyl trimethoxy, gamma-aminopropyl-triethoxy Silane, acrylic triethoxysilane and vinyltriacetoxy silane.
Photoinitiator is preferably Irgacure 184 (Ciba-Gaigey companies of Switzerland) and/or photoinitiator Darocure 1173 (Ciba-Gaigey companies of Switzerland).
Corrosion inhibiter is preferably selected from organic fluorocompound " Zonyl " series of products of du pont company, preferably Zonyl FSG.
Preferably, light curing resin composition of the invention includes：
Light curing resin composition of the invention preferably further includes：
The weight portion of corrosion inhibiter 0.08~0.12.
Corrosion inhibiter is preferably selected from organic fluorocompound " Zonyl " series of products of du pont company, preferably Zonyl FSG, Or apply 0.2wt%S217.
Described photocured cross-linked dose is preferably selected from triethylene-glycol diacrylate (TEGDA), tetraethylene-glycol two Acrylate (TTGDA), diethylene glycol diacrylate (DEGDA).
The preparation method of light curing resin composition of the invention includes uniformly mixing above-mentioned various composition.
The present invention still further provides is used for the quick method for repairing aircraft non-bearing covering, the party using above-mentioned composition Method includes that dipping fibre reinforced materials (preferred high strength glass fibre, such as glass fabric) is made flexible prepreg and repairs benefit Piece, destruction damage zone is subsidized with the method for bonding, is solidified rapidly under the irradiation of ultraviolet light.
Above-mentioned high strength glass fiber includes：1) alkali-free glass fibre (E- glasses, Electrical Glass Fiber), Wherein alkali metal oxide content is 0-2%, main composition containing aluminoborosilicate, with good electrical insulating property, water resistance, machine Tool intensity is all relatively good.It is mainly used as electrically insulating material and fiberglass, engineering material, rubber etc. reinforcing material.2) alkali glass in Glass fiber (C- glasses, Chemical Glass Fiber), wherein alkali metal oxide content are 8-12% or so, main calcic Sodium silicate composition, with good acid resistance, mechanical strength is 75% or so of alkali-free glass fibre, is mainly used in latex cloth With the base material of window screening, it is also possible to make acid filter cloth and the reinforcing material less high for electrical property, intensity requirement.Additionally, Its cost is less than alkali containing glass fibre.3) high alkali glass fibre (A- glasses, Alkali Glass Fiber), wherein alkali metal oxygen Compound content is 14-17% or so, main calcic sodium silicate composition.Because its alkalinity is higher, thus mechanical strength compared with Difference, water resistance is poor, and acid resistance is good.Its raw material sources is convenient, with low cost, can as battery spacer, pipeline wrapping cloth, Asphalt felt base fabric etc..4) special glass fibre, chemical composition is adapted to the fiber of special purpose, such as high elastic modulus glass fibre (M- glasses), introduces BeO, Li2O、ZrO2、TiO2；Radiation proof glass, introduces PbO, ZrO2、Ta2O3、WO3Deng.
Advantages of the present invention
The present invention can quickly repair the broken hole at aircraft non-bearing position, aircraft skin operation is completed in a short time and is robbed Repair, and with sufficient adhesive strength.
Specific embodiment
The present invention is illustrated below by way of specific embodiment.
Synthesis example 1
In (cleaning) the 500ml there-necked flask equipped with thermometer, electric mixer and reflux condensing tube, add 70ml toluene, adds 90g E-51 and 60g E-44, and dissolve (about needs to stir 10-15min) under agitation completely.Addition 0.1g pairs Benzenediol and 1.2g triethylamines.It is heated to 75-80 DEG C and keeps constant temperature, start that 65g acrylic acid is added dropwise, dropwise addition per minute is about 35-40 drops.Completion of dropping, is warmed up to 105-110 DEG C, continues to react 2h.Reaction is finished, and is cooled to 40-50 DEG C, by reaction unit Vacuum distillation apparatus are changed to, vacuum distillation removes solvent under about 50-100Pa vacuums.(note：Vacuum distillation for true Reciprocal of duty cycle is not particularly limited, and vacuum is lower, and temperature needed for distillation heating is lower).Remove the residue after solvent and be propylene Sour modified epoxy prepolymer, viscosity about 18.5Pa.s.
Synthesis example 2
E-54 replace embodiment 1 in E-51 (90g E-55 and 60g E-44 replace embodiment 1 in 90g E-51 and 60gE-44), 70g α-methacrylic acids replace 65g acrylic acid therein；Other reaction conditions and vacuum distillation condition are all identical, Prepare α-methacrylic acid modified epoxy prepolymer.The optic-solidified adhesive bonding impregnated glass fiber cloth of preparation, is bonded duralumin Alloy, adhesive strength is up to 17.5MPa.
Contrast synthesis example 1
It is identical with synthesis example 1, simply individually use 150g E-51.
Contrast synthesis example 2
It is identical with synthesis example 1, simply individually use 150g E-54.
Contrast synthesis example 3
It is identical with synthesis example 1, only it is single use the E-44 of 150g.
Synthesis example 3
In a 500ml there-necked flask equipped with thermometer, electric mixer and reflux condensing tube, 80g polyethers is added Glycol (N204, molecular weight 400, hydroxyl value 270-290mg KOH/g；Viscosity, 50-100mPa.s (25 DEG C) is commercially available), in stirring Lower addition 60ml TDI (toluene di-isocyanate(TDI)), 0.4g DBT (dibutyl tin laurate) and 0.25g stannous octoates.Heating To 80 DEG C, and constant temperature 2-2.5h at being maintained at 80-85 DEG C, obtain EU.Less than 40 DEG C are cooled to, 25g is added Dihydromethyl propionic acid and 60g E-51, viscosity is adjusted with proper amount of acetone.More than 65 DEG C are heated to, and are maintained at 65-70 DEG C Reaction 1h.50 DEG C are cooled to, 0.015g hydroquinones is added, 0.2g DBT are heated to more than 60 DEG C, 32g acrylic acid hydroxyls are added dropwise Propyl ester (in or so half an hour completion of dropping), and 2h is reacted at being maintained at 65-70 DEG C.40 DEG C are cooled to bottom discharge, are obtained final product " polyurethane modified epoxy resin (acrylate) prepolymer ".Viscosity 16.2Pa.s.
Synthesis example 4
Replace the E-51 in synthesis example 3 with the composition of E-51 and E-44.
Synthesis example 5
Dipropylene glycol 30g is used, instead of the 80g PTMEGs in synthetic example 3.
Synthesis example 6：The synthesis of polyurethane acrylate resin prepolymer
In a 500ml there-necked flask equipped with thermometer, electric mixer and reflux condensing tube, the poly- second of 100g is added Glycol 200 (molecular weight 200, commercially available), adds 65ml TDI (toluene di-isocyanate(TDI)), 0.35g DBT (February under agitation Dilaurylate) and 0.25g stannous octoates.It is heated to 80 DEG C, and constant temperature 2-3h at being maintained at 80-85 DEG C, obtain polyethers Type polyurethane.Less than 50 DEG C are cooled to, 0.05g hydroquinones is added, 55 DEG C are heated to, 50g hydroxypropyl acrylates are added dropwise (40 Minute or so completion of dropping), react 2h at being maintained at 55-60 DEG C.40 DEG C of dischargings are cooled to, polyurethane acrylate resin is obtained final product Prepolymer.
Contrast synthesis example 4
It is identical with synthesis example 3, simply replace E-51 using E-44.
Embodiment 1
Above composition is well mixed and is made light-cured resin viscose glue.The optic-solidified adhesive impregnated glass fiber cloth of preparation, glues Duralumin, hard alumin ium alloy is connect, adhesive strength is up to 18.5MPa.
Embodiment 2
It is same as Example 1, simply use the acrylic modified epoxy resin prepolymer of synthetic example 2.The light of preparation Solidification glue sticking impregnated glass fiber cloth, is bonded duralumin, hard alumin ium alloy, and adhesive strength reaches 17.5MPa.
Comparative example 1
With embodiment 1, the acrylic modified epoxy resin prepolymer of contrast synthesis example 1, the glue for as a result preparing simply are used Stick prepolymer adhesive strength is relatively low, is bonded duralumin, hard alumin ium alloy, and adhesive strength only has 16.5MPa.
Comparative example 2
With embodiment 1, the acrylic modified epoxy resin prepolymer of contrast synthesis example 2, the glue for as a result preparing simply are used Stick prepolymer adhesive strength is relatively low, is bonded duralumin, hard alumin ium alloy, and adhesive strength only has 16.2MPa.
Comparative example 3
With embodiment 1, simply using the acrylic modified epoxy resin prepolymer of contrast synthesis example 3, as a result gained light is consolidated Change resin viscose glue E-44 levelabilities poor, it is impossible to even spread.
Embodiment 3
Above composition is well mixed and is made light-cured resin viscose glue.
Compared with the epoxy acrylic ester prepolymer in embodiment 1, embodiment 2, the polyurethane modified epoxy of the present embodiment More preferably, optic-solidified adhesive macromolecular chain is flexible for resin (acrylate) prepolymer corrosion resistance, and the volume of adhesive is received after photocuring Shrinkage very little.But, the adhesive strength (bonding duralumin, hard alumin ium alloy) of the optic-solidified adhesive is than light that epoxy acrylic ester prepolymer is prepared Solidification glue is lower slightly, about 16.5MPa.But, compared with epoxy acrylic ester prepolymer, resistance to 5wt%NaCl aqueous solution soakings are drawn Etching time extension more than the 5-6h for rising, reaches about 8-10h.
Embodiment 4
It is same as Example 3, simply replace the polyurethane of synthesis example 3 using the polyurethane modified epoxy resin of synthesis example 4 Modified epoxy, optic-solidified adhesive adhesive strength (being synthesized with the composition of E-51 and E-44 than synthetic example 1 of preparation ) the low about 2MPa of optic-solidified adhesive that epoxy acrylic ester prepolymer is prepared, be 16.5MPa, but as described above, the present embodiment it is poly- More preferably, optic-solidified adhesive macromolecular chain is flexible, glue after photocuring for urethane modified epoxy (acrylate) prepolymer corrosion resistance The cubical contraction very little of stick.Compared with epoxy acrylic ester prepolymer, the corrosion that resistance to 5wt%NaCl aqueous solution soakings cause More than time lengthening 5-6h.
Embodiment 5
It is same as Example 3, simply use the polyurethane modified epoxy resin of synthesis example 5.The optic-solidified adhesive of preparation and conjunction Prepolymer into embodiment 3 is compared：The macromolecular chain flexibility of optic-solidified adhesive is lower slightly, adhesive strength about 1MPa high, up to about 17.5MPa。
Embodiment 6
It is similar to Example 3, by the pre- of the synthesis example 1 of the prepolymer of the synthesis example 6 of 37.5 weight portions and 37.5 weight portions Polymers is according to 1:1 mass ratio mixing, instead of the polyurethane modified epoxy resin of the synthesis example 3 of 75 weight portions, for preparing light Solidification glue.Compared with the optic-solidified adhesive that the prepolymer of synthetic example 1 is prepared, adhesive strength low about 1MPa, about 17.5MPa, but It is that the etching time that resistance to 5wt%NaCl aqueous solution soakings cause extends more than 4-5h.
Comparative example 4
It is similar to Example 3, simply replace the poly- of synthesis example 3 using the polyurethane modified epoxy resin of contrast synthesis example 4 Urethane modified epoxy.As a result, duralumin, hard alumin ium alloy, adhesive strength about 15.5MPa are bonded.
The test of high and low temperature resistance
1) high temperature resistant experiment, 80 ± 1 DEG C, 100 ± 1 DEG C of thermostatic drying chamber are respectively placed in by tens of of bond sample Interior, 5 changes of measure lap shear strength are taken out in baking every time after 8,12,16,20,24,48 hours.Due to temperature Raise, polymer bond strength will exponentially decline, so the bonding agent result of study according to forefathers for other application field It is contemplated that if bond toasts more than 24 at 100 ± 1 DEG C, adhesive strength reduces within 20%, or 80 ± 1 More than 48 are toasted at DEG C, adhesive strength reduces within 20%, then the desert that estimated bond is possible to resistance to 50 to 60 DEG C is high Warm at least one month was to 45 days.
2) cold test, by tens of refrigerators for being respectively placed in -20 ± 1 DEG C of bond sample, -40 ± 1 DEG C of freezing In circulating slot, freezing 24,48,72, until after 168 hours every time take out 5 measure lap shear strength changes.
It is respectively provided with 60 DEG C and 100 DEG C of two high temperature, and -18 DEG C and -40 DEG C of two cryogenic conditions.Embodiment 1 Bond adhesive strength result of variations after 60 DEG C of lasting placement a period of times is shown in Table 2；The bond of embodiment 4 continues at 60 DEG C Adhesive strength result of variations is shown in Table 3 after placing a period of time.The adhesive strength result of variations after 100 DEG C of lasting placement a period of times It is shown in Table 4；Type discharge postpones the change test result of adhesive shear strength and is shown in Table 5 at -18 DEG C；Type discharge postpones bonding at -40 DEG C The change test result of shear strength is shown in Table 6.
The bond of the embodiment 1 of table 2 adhesive strength result of variations (2 layers of glass of bonding after 60 DEG C of lasting placement a period of times Glass fiber cloth)
Temperature (DEG C) Standing time (h) Maximum, force (Fm) Drawing crack area (cm2) 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
The bond of the embodiment 4 of table 3 adhesive strength result of variations (2 layers of glass of bonding after 60 DEG C of lasting placement a period of times Glass fiber cloth)
Temperature (DEG C) Standing time (h) Maximum, force (Fm) Drawing crack area (cm2) 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
Adhesive strength result of variations (the 2 layers of glass fabric of bonding) after 100 DEG C of lasting placement a period of times of table 4
Type discharge postpones the change test result (2 layers of glass fabric of bonding) of adhesive strength at 5-18 DEG C of table
Type discharge postpones the change test result (2 layers of glass fabric of bonding) of adhesive shear strength at 6-40 DEG C of table
From table 2 and table 3, the optic-solidified adhesive bond of embodiment 1,4 does not almost have in 60 DEG C of continuous more than 48h that place Cause being remarkably decreased for adhesive strength；48h is persistently placed at -18 DEG C and causes the change of adhesive strength also very little, it is real until 72h The bond shear strength for applying example 1 declines only 10%, and the bond shear strength of embodiment 4 does not almost decline and (is shown in Table 5).As can be seen from Table 4, or even under 100 DEG C of thermal extremes 12h is placed, the bond shear strength of embodiment 1 declines very little (2%), the bond shear strength of embodiment 4 declines about 10%；And 72h is placed under -40 DEG C of extreme low temperature, embodiment 1 Bond shear strength decline very little (3%), the bond shear strength of embodiment 4 is almost unchanged (being shown in Table 6).Illustrate to implement The bond resistance to elevated temperatures of example 1 is more excellent, and the bond resistance to low temperature of embodiment 4 is especially excellent.
Not only exposure can be smoothed out the solidification of optic-solidified adhesive to embodiment 1,4 at 100 DEG C, in a low temperature of -40 DEG C Also the solidification of optic-solidified adhesive can be smoothed out.
High wind tunnel testing
In order to the high velocity air that the anti-propeller for further investigating optic-solidified adhesive sticking patch under normal flight conditions causes impacts The phenomenon of bonding damage layer may be caused, it is on the other hand whether bad to the flowing generation of in-flight air-flow also for sticking patch is investigated Influence, has carried out wind tunnel test, test method normative reference：GJB (national military standard) 4008-2000 " aircraft external store high-speed wind tunnels Testing regulations ".The triplex glass fiber cloth being bonded using embodiment 1 and the composition of embodiment 3 is tried with the bond of duralumin, hard alumin ium alloy Sample experience 0.8,1.2 and 1.5 Mach (900,1300,1600km/h) across, surpass the continuous wind of two velocity of sound wind-tunnel, the time is respectively all After for 24h, there is not the phenomenon that abutting edge is peeled off or loosened；And for 5cm X 5cm, 15cm X 15cm and 25cm X For tri- sticking patch of size of 25cm, any influence for all not producing instrument detectable on the proper flow of air-flow.

Claims (12)

1. a kind of for the quick light curing resin composition repaired of aircraft non-bearing covering, said composition includes：
Photosensitive prepolymer acrylic modified epoxy resin prepolymer or polyurethane modified epoxy resin prepolymer 65-85 weight portions,
Photoinitiator 2-6 weight portions,
Photosensitive diluent 10-15 weight portions,
Photocured cross-linked dose of 4-6 weight portion,
Silane coupler 0.3-0.6 weight portions；
The photosensitive prepolymer acrylic modified epoxy resin prepolymer is by liquid epoxies E-51 and both E-44 Composition, or application liquid epoxies E-54 is adding with E-44 combinations thing with acrylic acid or α-methacrylic acid Reacted and synthesized under heat；The weight ratio of liquid epoxies E-51 and E-44 is 1 ~ 3:1 ~ 3, liquid epoxies E-54 with The weight ratio of E-44 is 1 ~ 3:1~3；
Or,
The polyurethane modified epoxy resin prepolymer is the polyurethane modified epoxy resin prepolymer for obtaining in the following manner： With E-51 or E-54 liquid epoxies base-materials, PTMEG and di-isocyanate reaction are allowed, prepare the poly- ammonia of polyether-type of intermediate 1 Ester；Intermediate 1 then reacts or the 1-3 with E-51 and/or E-54 and E44 with E-51 or E-54：The mixture reaction of 1-3, Obtain the polyurethane modified epoxy resin of intermediate 2；Intermediate 2 finally reacts with acrylic acid hydroxy alkyl ester, the corresponding poly- ammonia of generation Ester modified epoxy prepolymer.
2. light curing resin composition according to claim 1, it includes：
Photosensitive prepolymer acrylic modified epoxy resin prepolymer or polyurethane modified epoxy resin prepolymer 75-80 weight portions,
Photoinitiator 3-4 weight portions,
Photosensitive diluent Hexyl 2-propenoate and butyl methacrylate volume ratio 0.5 ~ 1.5:0.5 ~ 1.5 mixture 11-14 weights Amount part,
Photocured cross-linked dose of 4.5 ~ 5 weight portions,
Silane coupling agent vinyl triethoxysilane and/or vinyltrimethoxy silane 0.4-0.5 weight portions.
3. light curing resin composition according to claim 1, it is further included：
The weight portion of corrosion inhibiter 0.05 ~ 0.25.
4. light curing resin composition according to claim 2, it is further included：
The weight portion of corrosion inhibiter 0.08 ~ 0.12.
5. the light curing resin composition according to any one of claim 1-4, wherein, photoinitiator is Irgacure 184 or photoinitiator Darocure 1173.
6. light curing resin composition according to claim 5, wherein, corrosion inhibiter has selected from the fluorine-containing of du pont company Machine thing Zonyl series of products.
7. light curing resin composition according to claim 6, wherein, corrosion inhibiter is selected from the Zonyl of du pont company FSG。
8. the light curing resin composition according to any one of claim 1-4, wherein, photocured cross-linked dose selected from two contractings Triethylene glycol diacrylate（TEGDA）, Tetraethylene glycol diacrylate（TTGDA）, or diethylene glycol diacrylate （DEGDA）.
9. light curing resin composition according to claim 5, wherein, photocured cross-linked dose is selected from triethylene-glycol two Acrylate（TEGDA）, Tetraethylene glycol diacrylate（TTGDA）, or diethylene glycol diacrylate（DEGDA）.
10. light curing resin composition according to claim 6, wherein, photocured cross-linked dose is selected from triethylene-glycol Diacrylate（TEGDA）, Tetraethylene glycol diacrylate（TTGDA）, or diethylene glycol diacrylate（DEGDA）.
11. prepare the light curing resin composition method any one of claim 1-10, and methods described includes will be described Composition uniformly mixes.
Light curing resin composition any one of 12. usage rights requirement 1-10 is used for quick aircraft non-bearing of repairing and covers The method of skin, the method includes that dipping fibre reinforced materials is made flexible prepreg repaired patch, is subsidized with the method for bonding Destruction damage zone, solidifies rapidly under the irradiation of ultraviolet light.
CN201610580161.1A 2016-07-21 2016-07-21 A kind of light curing resin composition quickly repaired for aircraft non-bearing covering Expired - Fee Related CN106085263B (en)

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