CN103242767A - High-temperature-resistant bismaleimide resin carrier structure adhesive film and preparation method thereof - Google Patents
High-temperature-resistant bismaleimide resin carrier structure adhesive film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-temperature-resistant bismaleimide resin carrier structure adhesive film and a preparation method thereof, and relates to a high-temperature curing high-temperature-resistant structure adhesive. The invention aims to solve the problems that the conventional bismaleimide adhesive film does not have high temperature-resistant grade and high toughness. The adhesive film consists of bismaleimide resin, a technical modifier, a toughening modifier, a compatibilizer and a thixotropic agent. The preparation method comprises the following steps of: performing prepolymerization on the bismaleimide resin and the technical modifier to obtain a bismaleimide resin prepolymer; mixing the bismaleimide resin prepolymer, the toughening modifier, the compatibilizer and the thixotropic agent uniformly by a mechanical blending method to prepare an adhesive material; and preparing the adhesive by using a three-roller coating film-making machine under the film-forming assistance of the carrier. The adhesive has the characteristics of high-temperature resistance and high toughness, wherein the glass-transition temperature reaches above 280 DEG C and the honeycomb roller peeling strength reaches about 75.0 N.m/m. The adhesive is applied to adhesion of metal or composite material high-temperature-resistant structure members in the field of aerospace.
Description
Technical field
The present invention relates to the agent of hot setting high-temperature-resistant structure gluing, be specifically related to a kind of high temperature resistant bimaleimide resin carrier structure glued membrane and preparation method thereof.
Background technology
Structural adhesive is a kind of sizing agent that glueds joint for load bearing structure, and it can transmit bigger static state, dynamic load, and work that can be reliably and with long-term in environment for use.With respect to pasty state structural adhesive and solvent-borne type structural adhesive, advantages such as bondline thickness homogeneous and controllable, fugitive constituent are low because having for the membrane structure sizing agent, high strength, high tenacity, high-durability and high reliability have obtained to be extensive use of at aerospace field.
Because pure bimaleimide resin cured product cross-linking density is big, though temperature tolerance is high, therefore but processing performance and toughness are relatively poor, self neither possess the toughness reguirements that filming condition also can't satisfy structural film adhesive, it are carried out the film-forming process modification and toughening modifying is gordian technique.Existing bimaleimide resin structural film adhesive generally adopts the allyl group dihydroxyphenyl propane to 4,4 '-two amido ditane type bimaleimide resins (BDM type bimaleimide resin) carry out the copolymerization modification and improve its processing performance, adopt the second phase (thermosetting resin then, thermoplastic resin or rubber) it is carried out outer toughening modifying, be separated by solidification process and produce two phase structure and reach toughening effect, be subjected to the toughner molecular weight, curing process and curing reaction Kinetics influence, it is often not thorough to be separated, therefore the decline of the thermotolerance of sizing agent and modulus is bigger, and toughness reinforcing reliability also is subjected to certain influence.
At present, have commercial bismaleimides structural film adhesive both at home and abroad, but all do not have concurrently high temperature resistant and the high tenacity characteristic, second-order transition temperature as the ReduxHP655 span glued membrane of Hexcel company has reached 297.4 ℃, but honeycomb sandwich construction drum peel intensity only is 37.80N.m/m (aluminum alloy outer cover/aluminum alloy honeycomb); The service temperature of the span glued membrane of the HysolEA9673 of Henkel company can reach 288 ℃, but honeycomb sandwich construction drum peel intensity is 20.2N.m/m(aluminum alloy outer cover/aluminium honeycomb), domestic only have kind of the J-188 of Institute of Petrochemistry, HLJ Academy of Science span glued membrane, its second-order transition temperature only is about 210 ℃, the life-time service temperature is below 200 ℃, and honeycomb sandwich construction drum peel intensity (aluminum alloy outer cover/aluminium honeycomb) is 35.0N.m/m.
Summary of the invention
The objective of the invention is not have high-temperature resistant grade and high tenacity concurrently in order to solve existing bismaleimides glued membrane, and the problem that the processing performance difference can't the big area paving.And provide a kind of high temperature resistant bimaleimide resin carrier structure glued membrane and preparation method thereof.
A kind of high temperature resistant bimaleimide resin carrier structure glued membrane of the present invention is to be made by thixotropic agent and the carrier of 75～100 parts bimaleimide resin, 50～75 parts process modification agent, 10～25 parts plasticized modifier, 1～4 part of expanding material and 1～4 part according to mass fraction; Wherein, described bimaleimide resin is to be that the ratio of 5:3:2 is formed by the high temperature resistant short chain bimaleimide resin of BMT type, 4,4 '-two amido ditane type bimaleimide resins and ether-containing key 44DADPE type bismaleimides in mass ratio.
The preparation method of a kind of high temperature resistant bimaleimide resin carrier structure glued membrane of the present invention carries out according to following steps: the thixotropic agent that, takes by weighing 75～100 parts bimaleimide resin, 50～75 parts process modification agent, 10～20 parts of plasticized modifiers, 1～4 part of expanding material and 1～4 part by mass fraction; Two, the bimaleimide resin that step 1 is taken by weighing and process modification agent obtain copolymerization modification bismaleimide resin after joining in the reactor under whipped state heat temperature raising to 135～145 ℃ and being incubated 20～30 minutes; Three, the expanding material that step 1 is taken by weighing is dissolved in dehydrated alcohol to make solid content is 5% ethanolic soln, add the toughner that step 1 takes by weighing then, disperseed 5～10 minutes with 800～1000 rev/mins stir speed (S.S.) again, remove dehydrated alcohol and oven dry then, get the toughner after the processing; Four, adopt the mechanical blending method to mix the toughner of handling in the copolymerization modification bismaleimide resin that makes in the step 2 and the step 3, and then add the thixotropic agent that step 1 takes by weighing and continue to be blended into evenly, both obtained sizing material; Five, adopting three rollers to change under the auxiliary filming condition of carrier above-mentioned sizing material is coated with the film-making machine film forming, namely finishes the preparation of high temperature resistant bimaleimide resin carrier structure glued membrane; Wherein, described film-forming temperature is 70～90 ℃; The equipment of the described employing mechanical blending of step 4 is three-roll grinder or vacuum kneader; Described bimaleimide resin is to be that the ratio of 5:3:2 is formed by the high temperature resistant short chain bimaleimide resin of BMT type, 4,4 '-two amido ditane type bimaleimide resins and ether-containing key 44DADPE type bismaleimides in mass ratio.
The present invention comprises following beneficial effect:
The present invention adopts the bismaleimide resin mixture of different structure characteristics as matrix resin, adopting the heat resist modification agent is the process modification material, be toughner (adopting expanding material to its surface treatment) with inorganic and organic compound, be thixotropic agent with the inorganic nano-filler, be carrier with the fibrous braid, adopt copolymerization, the mechanical blending technology prepares sizing material, adopt three roller coat cloth film techniques to prepare a kind of modified bismaleimide resin glued membrane, have high temperature resistant, high tenacity, glued joint the reliability height, processing performance good etc. characteristics, can satisfy with bismaleimide resin based composites big area co-curing and glued joint requirement, be expected in the manufacturing of aerospace field refractory metal or composite material structural member, obtain to use.
1, it is matrix resin that the present invention has adopted three kinds of bismaleimide resin monomers, wherein based on high temperature resistant short chain bismaleimide resin (BMT), introduce part 4, the bimaleimide resin (44DADPE) of 4 '-two amido ditane type bimaleimide resins (BDM) and ether-containing key, the steric effect of its structure is given sizing agent high temperature resistant and high tenacity characteristics preferably, unite and adopted allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane are as the process modification agent, the modification bismaleimide resin that makes has high temperature resistant and characteristics good manufacturability, and the second-order transition temperature of sizing agent has reached about 280 ℃; Resin can soften the fusion film forming under 60～100 ℃, the sizing agent processing performance is good;
2, to adopt the inorganic and organic toughner of associating that sizing agent is carried out toughness reinforcing in the present invention, and adopt expanding material to handle to its surface, increases it and be combined and cohesive strength with the interface of interlaminar resin.Adopt the advantage of inorganic toughness reinforcing sizing agents such as super fiber, inorganic salt whisker and nanometer powder to be: it has concurrently toughness reinforcing and enhancement to sizing agent, this point is that organic toughner is incomparable, have certain contribution to improving second-order transition temperature, make that sizing agent second-order transition temperature of the present invention can be up to 280 ℃ about.The present invention is different from the toughening technology that other polymer toughening sizing agents are separated, the homogeneous system that adopts second-order transition temperature to differ bigger two kinds of thermoplastic resins is carried out toughness reinforcing through the ultrafine powder of pulverize at low temperature preparation to sizing agent, as adopt the ultrafine powder of polyetherimide and two kinds of thermoplastic resin preparations of polyamidoimide toughness reinforcing, the second-order transition temperature that polyetherimide is lower can heat up to solidify in the engineering and fuse the stronger interface cohesive force of formation mutually with modification bismaleimide resin system at sizing agent on the one hand, played compatibilization preferably, polyamidoimide in the homogeneous system does not take place to change mutually because having higher glass transition temperature on the other hand, this island structure with interface compatibilization is the basis that sizing agent of the present invention obtains higher toughness, has improved the toughness of sizing agent greatly.Unite organic and inorganic toughner and sizing agent is given tough, make it have high-temperature resistant grade and high tenacity characteristics concurrently, its second-order transition temperature has reached about 280 ℃, and (the glued membrane area density is 244g/m to sizing agent
2)-55 ℃ of shearing resistances reached about 15.0MPa; The normal temperature shearing resistance has reached more than the 18.0MPa, and 260 ℃ have reached 15.0MPa, still keeps about 13.0 under 288 ℃, and about 5.0MPa, (the glued membrane area density is 390g/m to sizing agent under 316 ℃
2) glued joint aluminium honeycomb sandwich construction drum peel intensity and reached 75N.m/m, ((the glued membrane area density is 390g/m to sizing agent
2)) glued joint aluminium honeycomb planar stretch intensity and reached more than the 5.0MPa.
Description of drawings
Fig. 1 is the DSC graphic representation of the test 1 high temperature resistant bimaleimide resin carrier structure glued membrane that makes.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: a kind of high temperature resistant bimaleimide resin carrier structure glued membrane of present embodiment is to be made by thixotropic agent and the carrier of 75～100 parts bimaleimide resin, 50～75 parts process modification agent, 10～25 parts plasticized modifier, 1～4 part of expanding material and 1～4 part according to mass fraction; Wherein, described bimaleimide resin is to be that the ratio of 5:3:2 is formed by the high temperature resistant short chain bimaleimide resin of BMT type, 4,4 '-two amido ditane type bimaleimide resins and ether-containing key 44DADPE type bismaleimides in mass ratio.
The BMT type bimaleimide resin of present embodiment is the commercially available prod, and its chemical structural formula is as follows,
The 44DADPE type bimaleimide resin of present embodiment be according to (Zhu Yulong, Yu Xinhai. novel ether-containing key bismaleimides synthetic, insulating material [J], 2005 (5): 6～8) disclosed method is prepared, its chemical structural formula is as follows:
Present embodiment comprises following beneficial effect:
Present embodiment adopts the bismaleimide resin mixture of different structure characteristics as matrix resin, adopting high temperature resistant copolymerization properties-correcting agent is the process modification material, be toughner (adopting expanding material to its surface treatment) with inorganic and organic compound, be thixotropic agent with the inorganic nano-filler, be carrier with the fibrous braid, adopt prepolymerization, the mechanical blending technology prepares sizing material, adopt three roller coat cloth film techniques to prepare a kind of modified bismaleimide resin glued membrane, have high temperature resistant, high tenacity, glued joint the reliability height, processing performance good etc. characteristics, can satisfy with bismaleimide resin based composites big area co-curing and glued joint requirement, be expected in the manufacturing of aerospace field refractory metal or composite material structural member, obtain to use.
1, it is matrix resin that present embodiment has adopted three kinds of bismaleimide resin monomers, wherein based on high temperature resistant short chain bismaleimide resin (BMT), introduce part 4, the bimaleimide resin (44DADPE) of 4 '-two amido ditane type bimaleimide resins (BDM) and ether-containing key, the steric effect of its structure is given sizing agent high temperature resistant and high tenacity characteristics preferably, unite and adopted allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane are as properties-correcting agent, the modification bismaleimide resin that makes has high temperature resistant and characteristics good manufacturability, and the second-order transition temperature of sizing agent has reached more than 280 ℃; Resin can soften the fusion film forming under 60～100 ℃, the sizing agent processing performance is good;
2, to adopt the inorganic and organic toughner of associating that sizing agent is carried out toughness reinforcing for present embodiment, and adopt expanding material to handle to its surface, increases it and be combined and cohesive strength with the interface of interlaminar resin.Adopt the advantage of inorganic toughness reinforcing sizing agents such as super fiber, inorganic salt whisker and nanometer powder to be: it has concurrently toughness reinforcing and enhancement to sizing agent, this point is that organic toughner is incomparable, have certain contribution to improving second-order transition temperature, make that present embodiment sizing agent second-order transition temperature can be up to more than 280 ℃.Present embodiment is different from the toughening technology that other polymer toughening sizing agents are separated, the homogeneous system that adopts second-order transition temperature to differ bigger two kinds of thermoplastic resins is carried out toughness reinforcing through the ultrafine powder of pulverize at low temperature preparation to sizing agent, as adopt the ultrafine powder of polyetherimide and two kinds of thermoplastic resin preparations of polyamidoimide toughness reinforcing, the second-order transition temperature that polyetherimide is lower can heat up to solidify in the engineering and fuse the stronger interface cohesive force of formation mutually with modification bismaleimide resin system at sizing agent on the one hand, played compatibilization preferably, polyamidoimide in the homogeneous system does not take place to change mutually because having higher glass transition temperature on the other hand, this island structure with interface compatibilization is the basis that the present embodiment sizing agent obtains higher thermal toughness, has improved the toughness of sizing agent greatly.Unite organic and inorganic toughner and sizing agent is given tough, make it have high-temperature resistant grade and high tenacity characteristics concurrently, its second-order transition temperature has reached more than 280 ℃, and (the glued membrane area density is 244g/m to sizing agent
2)-55 ℃ of shearing resistances reached about 15.0MPa; The normal temperature shearing resistance has reached more than the 18.0MPa, and 260 ℃ have reached 15.0MPa, still keeps about 13.0 under 288 ℃, and about 5.0MPa, (the glued membrane area density is 390g/m to sizing agent under 316 ℃
2) glued joint aluminium honeycomb sandwich construction drum peel intensity and reached 75.0N.m/m, ((the glued membrane area density is 390g/m to sizing agent
2)) glued joint aluminium honeycomb planar stretch intensity and reached more than the 5.0MPa.
Embodiment two: what present embodiment and embodiment one were different is: described high temperature resistant bimaleimide resin carrier structure glued membrane is to be made by 80～90 parts bimaleimide resin, 55～70 parts of process modification agent, 15～20 parts plasticized modifier, 2～4 parts expanding material and 2～4 parts thixotropic agent and carrier according to mass fraction.Other are identical with embodiment one.
Embodiment three: what present embodiment was different with embodiment one or two is: described process modification agent is made up of allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane; The mass ratio of described allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane is 6:3:1.Other are identical with embodiment one or two.
Embodiment four: what present embodiment was different with one of embodiment one to three is: described plasticized modifier is made up of inorganic toughner and organic toughner, and wherein, the mass ratio of inorganic toughner and organic toughner is 1:5.Other steps are identical with one of embodiment one to three with parameter.
Embodiment five: what present embodiment was different with one of embodiment one to four is that described inorganic toughner is one or more mixtures formed by any ratio in super fiber, inorganic salt whisker, the inorganic nano powder; Wherein super fiber is single wall or multi-walled carbon nano-tubes, the inorganic salt whisker is one or more mixtures formed by any ratio in silicon carbide whisker, aluminium borate whisker or the calcium sulfate crystal whiskers, and the inorganic nano powder is one or more mixtures of forming by any ratio of silica powder, aluminium sesquioxide and titanium dioxide.Other steps are identical with one of embodiment one to four with parameter.
Embodiment six: what present embodiment was different with one of embodiment one to five is: described organic toughner prepares as follows: polyetherimide and polyamidoimide, phenolphthalein base polyaryletherketone and polyamidoimide or phenolphthalein base polyether sulphone and polyamidoimide be dissolved in remove solvent after forming homogeneous system in the trichloromethane solvent, adopt then Lowtemperaturepulverizer with its pulverizing and the ultrafine powder of crossing 270 mesh sieve as organic toughner; Wherein, the mass ratio of described polyetherimide and polyamidoimide is 1:4～5; The mass ratio of phenolphthalein base polyaryletherketone and polyamidoimide is 1:4～5; Phenolphthalein base polyether sulphone and polyamidoimide are 1:3～4 by mass ratio.Other steps are identical with one of embodiment one to five with parameter.
Embodiment seven: what present embodiment was different with one of embodiment one to six is: described expanding material by in γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-amino propyl trimethoxy silicane, vinyl trimethylsilane, the methyl tri-tert peroxy-silane one or more by arbitrarily than the mixture of forming.Other steps are identical with one of embodiment one to six with parameter.
Embodiment eight: what present embodiment was different with one of embodiment one to seven is: described thixotropic agent is by aerosil, organobentonite or asbestos powder.Other steps are identical with one of embodiment one to seven with parameter.
Embodiment nine: what present embodiment was different with one of embodiment one to eight is: described carrier is by glass fiber woven cloth, silica fibrage cloth or carbon fiber woven cloth.Other steps are identical with one of embodiment one to eight with parameter.
Embodiment ten: the preparation method of a kind of high temperature resistant bimaleimide resin carrier structure glued membrane of present embodiment is to carry out according to following steps: the thixotropic agent that, takes by weighing 75～100 parts bimaleimide resin, 50～75 parts process modification agent, 10～20 parts of plasticized modifiers, 1～4 part of expanding material and 1～4 part by mass fraction; Two, the bimaleimide resin that step 1 is taken by weighing and process modification agent obtain copolymerization modification bismaleimide resin after joining in the reactor under whipped state heat temperature raising to 135～145 ℃ and being incubated 20～30 minutes; Three, the expanding material that step 1 is taken by weighing is dissolved in dehydrated alcohol to make solid content is 5% ethanolic soln, add the toughner that step 1 takes by weighing then, disperseed 5～10 minutes with 800～1000 rev/mins stir speed (S.S.) again, remove dehydrated alcohol and oven dry then, get the toughner after the processing; Four, adopt the mechanical blending method to mix the toughner of handling in the copolymerization modification bismaleimide resin that makes in the step 2 and the step 3, and then add the thixotropic agent that step 1 takes by weighing and continue to be blended into evenly, both obtained sizing material; Five, adopting three rollers to change under the auxiliary filming condition of carrier above-mentioned sizing material is coated with the film-making machine film forming, namely finishes the preparation of high temperature resistant bimaleimide resin carrier structure glued membrane; Wherein, described film-forming temperature is 70～90 ℃; The equipment of the described employing mechanical blending of step 4 is three-roll grinder or vacuum kneader; Described bimaleimide resin is to be that the ratio of 5:3:2 is formed by the high temperature resistant short chain bimaleimide resin of BMT type, 4,4 '-two amido ditane type bimaleimide resins and ether-containing key 44DADPE type bismaleimides in mass ratio.
The BMT type bimaleimide resin of present embodiment is the commercially available prod, and its chemical structural formula is as follows,
The 44DADPE type bimaleimide resin of present embodiment be according to disclosed method (Zhu Yulong, Yu Xinhai. novel ether-containing key bismaleimides synthetic, insulating material [J], 2005 (5): 6～8) be prepared, its chemical structural formula is as follows:
Present embodiment comprises following beneficial effect:
Present embodiment adopts the bismaleimide resin mixture of different structure characteristics as matrix resin, adopting high temperature resistant copolymerization properties-correcting agent is the process modification material, be toughner (adopting expanding material to its surface treatment) with inorganic and organic compound, be thixotropic agent with the inorganic nano-filler, be carrier with the fibrous braid, adopt copolymerization, the mechanical blending technology prepares sizing material, adopt three roller coat cloth film techniques to prepare a kind of modified bismaleimide resin glued membrane, have high temperature resistant, high tenacity, glued joint the reliability height, processing performance good etc. characteristics, can satisfy with bismaleimide resin based composites big area co-curing and glued joint requirement, be expected in the manufacturing of aerospace field refractory metal or composite material structural member, obtain to use.
1, it is matrix resin that present embodiment has adopted three kinds of bismaleimide resin monomers, wherein based on high temperature resistant short chain bismaleimide resin (BMT), introduce part 4, the bimaleimide resin (44DADPE) of 4 '-two amido ditane type bimaleimide resins (BDM) and ether-containing key, the steric effect of its structure is given sizing agent high temperature resistant and high tenacity characteristics preferably, unite and adopted allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane are as properties-correcting agent, the copolymerization modification bismaleimide resin that makes has high temperature resistant and characteristics good manufacturability, and the second-order transition temperature of sizing agent has reached more than 280 ℃; Resin can soften the fusion film forming under 60～100 ℃, the sizing agent processing performance is good;
2, to adopt the inorganic and organic toughner of associating that sizing agent is carried out toughness reinforcing for present embodiment, and adopt expanding material to handle to its surface, increases it and be combined and cohesive strength with the interface of interlaminar resin.Adopt the advantage of inorganic toughness reinforcing sizing agents such as super fiber, inorganic salt whisker and nanometer powder to be: it has concurrently toughness reinforcing and enhancement to sizing agent, this point is that organic toughner is incomparable, have certain contribution to improving second-order transition temperature, make that present embodiment sizing agent second-order transition temperature can be up to more than 280 ℃.Present embodiment is different from the toughening technology that other polymer toughening sizing agents are separated, the homogeneous system that adopts second-order transition temperature to differ bigger two kinds of thermoplastic resins is carried out toughness reinforcing through the ultrafine powder of pulverize at low temperature preparation to sizing agent, as adopt the ultrafine powder of polyetherimide and two kinds of thermoplastic resin preparations of polyamidoimide toughness reinforcing, the second-order transition temperature that polyetherimide is lower can heat up to solidify in the engineering and fuse the stronger interface cohesive force of formation mutually with modification bismaleimide resin system at sizing agent on the one hand, played compatibilization preferably, polyamidoimide in the homogeneous system does not take place to change mutually because having higher glass transition temperature on the other hand, this island structure with interface compatibilization is the basis that the present embodiment sizing agent obtains higher thermal toughness, has improved the toughness of sizing agent greatly.Unite organic and inorganic toughner and sizing agent is given tough, make it have high-temperature resistant grade and high tenacity characteristics concurrently, its second-order transition temperature has reached more than 280 ℃, and (the glued membrane area density is 244g/m to sizing agent
2)-55 ℃ of shearing resistances reached about 15.0MPa; The normal temperature shearing resistance has reached more than the 18.0MPa, and 260 ℃ have reached 15.0MPa, still keeps about 13.0 under 288 ℃, and about 5.0MPa, (the glued membrane area density is 390g/m to sizing agent under 316 ℃
2) glued joint aluminium honeycomb sandwich construction drum peel intensity and reached 75.0N.m/m, ((the glued membrane area density is 390g/m to sizing agent
2)) glued joint aluminium honeycomb planar stretch intensity and reached more than the 5.0MPa.
Embodiment 11: what present embodiment and embodiment ten were different is: described process modification agent is made up of allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane; The mass ratio of described allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane is 6:3:1.Other steps are identical with embodiment ten with parameter.
Embodiment 12: what present embodiment was different with embodiment ten or 11 is: described plasticized modifier is made up of inorganic toughner and organic toughner, and wherein, the mass ratio of inorganic toughner and organic toughner is 1:5.
Other steps are identical with embodiment ten or 11 with parameter.
Embodiment 13: what present embodiment was different with one of embodiment ten to 12 is: described inorganic toughner is one or more mixtures formed by any ratio in super fiber, inorganic salt whisker, the inorganic nano powder; Wherein super fiber is single wall or multi-walled carbon nano-tubes, the inorganic salt whisker is one or more mixtures formed by any ratio in silicon carbide whisker, aluminium borate whisker or the calcium sulfate crystal whiskers, and the inorganic nano powder is one or more mixtures of forming by any ratio of silica powder, aluminium sesquioxide and titanium dioxide.Other steps are identical with one of embodiment ten to 12 with parameter.
Embodiment 14: what present embodiment was different with one of embodiment ten to 13 is: described organic toughner prepares as follows: polyetherimide and polyamidoimide, phenolphthalein base polyaryletherketone and polyamidoimide or phenolphthalein base polyether sulphone and polyamidoimide be dissolved in remove solvent after forming homogeneous system in the trichloromethane solvent, adopt then Lowtemperaturepulverizer with its pulverizing and the ultrafine powder of crossing 270 mesh sieve as organic toughner; Wherein, the mass ratio of described polyetherimide and polyamidoimide is 1:4～5; The mass ratio of phenolphthalein base polyaryletherketone and polyamidoimide is 1:4～5; Phenolphthalein base polyether sulphone and polyamidoimide are 1:3～4 by mass ratio.Other steps are identical with one of embodiment ten to 13 with parameter.
Embodiment 15: what present embodiment was different with one of embodiment ten to 14 is: described expanding material by in γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-amino propyl trimethoxy silicane, vinyl trimethylsilane, the methyl tri-tert peroxy-silane one or more by arbitrarily than the mixture of forming.Other steps are identical with one of embodiment ten to 14 with parameter.
Embodiment 16: what present embodiment was different with one of embodiment ten to 15 is: described thixotropic agent is by aerosil, organobentonite or asbestos powder.Other steps are identical with one of embodiment ten to 15 with parameter.
Embodiment 17: what present embodiment was different with one of embodiment ten to 16 is: described carrier is by glass fiber woven cloth, silica fibrage cloth or carbon fiber woven cloth.Other steps are identical with one of embodiment ten to 16 with parameter.
By following verification experimental verification beneficial effect of the present invention:
Test 1
The preparation method of a kind of high temperature resistant bimaleimide resin carrier structure glued membrane of this test is to carry out according to following steps: the thixotropic agent that, takes by weighing 100 parts bimaleimide resin, 75 parts process modification agent, 20 parts of plasticized modifiers, 3 parts of expanding materials and 3 parts by mass fraction; Two, the bimaleimide resin that step 1 is taken by weighing and process modification agent obtain copolymerization modification bismaleimide resin after joining in the reactor under whipped state heat temperature raising to 140 ℃ and being incubated 25 minutes; Three, the expanding material that step 1 is taken by weighing is dissolved in dehydrated alcohol to make solid content is 5% ethanolic soln, add the toughner that step 1 takes by weighing then, stirred 6 minutes with 900 rev/mins speed again, remove dehydrated alcohol and oven dry then, get the toughner after the processing; Four, adopt the mechanical blending method to mix the toughner of handling in the copolymerization modification bismaleimide resin that makes in the step 2 and the step 3, and then add the thixotropic agent that step 1 takes by weighing and continue to be blended into evenly, both obtained sizing material; Five, adopting three rollers to change under the auxiliary filming condition of carrier above-mentioned sizing material is coated with film forming on the film-making machine, namely finishes the preparation of high temperature resistant bimaleimide resin carrier structure glued membrane; Wherein, described film-forming temperature is 80 ℃; The equipment of the described employing mechanical blending of step 4 is three-roll grinder.
Process modification agent described in this test is made up of allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane; The mass ratio of described allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane is 6:3:1;
Described bimaleimide resin is by the high temperature resistant short chain bimaleimide resin of BMT type, 4, the bismaleimide resin of 4 '-two amido ditane type bimaleimide resins (BDM) and 44DADPE type ether-containing key is formed, and three's consumption is counted the high temperature resistant short chain bimaleimide resin of BMT type by mass ratio: the bismaleimide resin=5:3:2 of BDM:44DADPE type ether-containing key;
Described plasticized modifier is made up of by mass ratio 1:5 inorganic and organic toughner, wherein inorganic toughner is that multi-walled carbon nano-tubes and silicon carbide whisker are the ratio composition of 1:3 in mass ratio, organic toughner prepares as follows: be that 1:4.5 is dissolved in and removes solvent after forming homogeneous system in the trichloromethane methane with polyetherimide and polyamidoimide by mass ratio, adopt the low-temperature airflow pulverizer then with its pulverizing and cross ultrafine powder that 270 mesh sieve obtain as organic toughner;
Described expanding material is γ-glycidyl ether oxygen propyl trimethoxy silicane;
Described thixotropic agent is aerosil;
Described carrier is glass fiber woven cloth, and specification is 25g/m
2
The DSC curve of the high temperature resistant bimaleimide resin carrier structure glued membrane that this test makes as shown in Figure 1, as seen from Figure 1: the reaction heating of sizing agent is the steamed bun peak, reacting initial temperature is about 172.3 ℃, the reaction summit temperature is 247.6 ℃, the reaction end temp is at 334.7 ℃, solidification range is wideer, can be complementary with bismaleimide resin based composites curing process window, and can satisfy two kinds of co-curing technologies: 1. 125 ℃ stopped 1 hour down, 175 ℃ solidify down 4 hours+200 ℃ and solidified 1 hour, 230 ℃ of aftertreatments 4 hours; 2. 125 ℃ stopped 1 hour down, and 175 ℃ solidified 4 hours down, and 200 ℃ solidified 1 hour+260 ℃ following aftertreatments of 230 ℃ of following aftertreatments 4 hours 1 hour.The former curing process is adopted in this test.
High tenacity bimaleimide resin carrier structure glued membrane to this test preparation carries out the test of mechanical property, and the titanium alloy test piece is adopted in test.Test result: the second-order transition temperature of sizing agent cured product has reached 283.6 ℃, and (the glued membrane area density is 244g/m to sizing agent
2)-55 ℃ of shearing resistances reached about 15.4MPa; The normal temperature shearing resistance has reached more than the 19.6MPa, and 260 ℃ have reached 14.8MPa, still keeps about 13.4 under 288 ℃, and about 4.9MPa, (the glued membrane area density is 390g/m to sizing agent under 316 ℃
2) glued joint aluminium honeycomb sandwich construction drum peel intensity and reached 78.1N.m/m, ((the glued membrane area density is 390g/m to sizing agent
2)) glued joint aluminium honeycomb planar stretch intensity and reached more than the 4.2MPa.
Testing method: GJB1709-1993 tackiness agent cryogenic tensile shearing resistance measuring method; GB/T7124-2008 tackiness agent Determination of The Tensile Shearing Strength; GJB444-1988 tackiness agent drawing by high temperature shear strength test method; GJB130.7-1986 glueds joint aluminium honeycomb sandwich construction drum peel test method; GJB130.4-1986 glueds joint aluminium honeycomb sandwich construction planar stretch test method.
Test 2
The preparation method of a kind of high temperature resistant bimaleimide resin carrier structure glued membrane of this test is to carry out according to following steps: the thixotropic agent that, takes by weighing 90 parts bimaleimide resin, 70 parts process modification agent, 15 parts of plasticized modifiers, 2 parts of expanding materials and 3 parts by mass fraction; Two, the bimaleimide resin that step 1 is taken by weighing and process modification agent obtain copolymerization modification bismaleimide resin after joining in the reactor under whipped state heat temperature raising to 145 ℃ and being incubated 20 minutes; Three, the expanding material that step 1 is taken by weighing is dissolved in dehydrated alcohol to make solid content is 5% ethanolic soln, add the toughner that step 1 takes by weighing then, stirred 8 minutes with 1000 rev/mins speed again, remove dehydrated alcohol and oven dry then, get the toughner after the processing; Four, adopt the mechanical blending method to mix the toughner of handling in the copolymerization modification bismaleimide resin that makes in the step 2 and the step 3, and then add the thixotropic agent that step 1 takes by weighing and continue to be blended into evenly, both obtained sizing material; Five, adopting three rollers to change under the auxiliary filming condition of carrier above-mentioned sizing material is coated with film forming on the film-making machine, namely finishes the preparation of high temperature resistant bimaleimide resin carrier structure glued membrane; Wherein, described film-forming temperature is 75 ℃; The equipment of the described employing mechanical blending of step 4 is three-roll grinder.
Process modification agent described in this test is made up of allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane; The mass ratio of described allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane is 6:3:1;
Described bimaleimide resin is by the high temperature resistant short chain bimaleimide resin of BMT type, 4, the bismaleimide resin of 4 '-two amido ditane type bimaleimide resins (BDM) and 44DADPE type ether-containing key is formed, and three's consumption is pressed the high temperature resistant short chain bimaleimide resin of mass ratio BMT type: the bismaleimide resin=5:3:2 of BDM:44DADPE type ether-containing key;
Described plasticized modifier is made up of by mass ratio 1:5 inorganic and organic toughner, wherein inorganic toughner is that silicon carbide whisker and titanium dioxide are the ratio composition of 1:1 in mass ratio, organic toughner prepares as follows: be that 1:3.5 is dissolved in and removes solvent after forming homogeneous system in the trichloromethane methane with phenolphthalein base polyether sulphone and polyamidoimide by mass ratio, adopt the low-temperature airflow pulverizer then with its pulverizing and cross ultrafine powder that 270 mesh sieve obtain as organic toughner;
Described expanding material is γ-glycidyl ether oxygen propyl trimethoxy silicane;
Described thixotropic agent is aerosil;
Described carrier is glass fiber woven cloth, and specification is 25g/m
2
High temperature resistant bimaleimide resin carrier structure glued membrane to this test preparation carries out the test of mechanical property, and being glued material is bismaleimide resin/carbon-fibre composite and prepreg thereof, adopts the two lap shear test specimens of autoclave co-curing adhesive technology preparation.Curing process: 125 ℃ stopped 1 hour down, and 175 ℃ solidified 4 hours down, and 200 ℃ solidified 1 hour+260 ℃ following aftertreatments of 230 ℃ of following aftertreatments 4 hours 1 hour.Test material preparation is undertaken by the BMS5-154E standard, and the two lap shear test of tackiness agent are undertaken by the BSS7202 method.
Test result: the high tenacity bimaleimide resin carrier structure glued membrane-55 ℃ down cut intensity of this test preparation has reached 15.0MPa, the normal temperature shearing resistance can reach 18.7MPa, 260 ℃ of shearing resistances can reach 14.2MPa, and 288 ℃ of shearing resistances have reached 12.5MPa.
Claims (10)
1. high temperature resistant bimaleimide resin carrier structure glued membrane is characterized in that high temperature resistant bimaleimide resin carrier structure glued membrane is to be made by thixotropic agent and the carrier of 75～100 parts bimaleimide resin, 50～75 parts process modification agent, 10～25 parts plasticized modifier, 1～4 part of expanding material and 1～4 part according to mass fraction; Wherein, described bimaleimide resin is to be that the ratio of 5:3:2 is formed by the high temperature resistant short chain bimaleimide resin of BMT type, 4,4 '-two amido ditane type bimaleimide resins and ether-containing key 44DADPE type bismaleimides in mass ratio.
2. a kind of high temperature resistant bimaleimide resin carrier structure glued membrane according to claim 1 is characterized in that described high temperature resistant bimaleimide resin carrier structure glued membrane is to be made by 80～90 parts bimaleimide resin, 55～70 parts of process modification agent, 15～20 parts plasticized modifier, 2～4 parts expanding material and 2～4 parts thixotropic agent and carrier according to mass fraction.
3. a kind of high temperature resistant bimaleimide resin carrier structure glued membrane according to claim 1 and 2 is characterized in that described process modification agent is made up of allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane; The mass ratio of described allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane is 6:3:1.
4. a kind of high temperature resistant bimaleimide resin carrier structure glued membrane according to claim 1 and 2, it is characterized in that described plasticized modifier is made up of inorganic toughner and organic toughner, wherein, the mass ratio of inorganic toughner and organic toughner is 1:5.
5. according to claims 4 described a kind of high temperature resistant bimaleimide resin carrier structure glued membranes, it is characterized in that described inorganic toughner is one or more mixtures formed by any ratio in super fiber, inorganic salt whisker, the inorganic nano powder; Wherein super fiber is single wall or multi-walled carbon nano-tubes, the inorganic salt whisker is one or more mixtures formed by any ratio in silicon carbide whisker, aluminium borate whisker or the calcium sulfate crystal whiskers, and the inorganic nano powder is one or more mixtures of forming by any ratio of silica powder, aluminium sesquioxide and titanium dioxide.
6. according to claims 4 described a kind of high temperature resistant bimaleimide resin carrier structure glued membranes, it is characterized in that described organic toughner prepares as follows: polyetherimide and polyamidoimide, phenolphthalein base polyaryletherketone and polyamidoimide or phenolphthalein base polyether sulphone and polyamidoimide be dissolved in remove solvent after forming homogeneous system in the trichloromethane solvent, adopt then Lowtemperaturepulverizer with its pulverizing and the ultrafine powder of crossing 270 mesh sieve as organic toughner; Wherein, the mass ratio of described polyetherimide and polyamidoimide is 1:4～5; The mass ratio of phenolphthalein base polyaryletherketone and polyamidoimide is 1:4～5; Phenolphthalein base polyether sulphone and polyamidoimide are 1:3～4 by mass ratio.
7. a kind of high temperature resistant bimaleimide resin carrier structure glued membrane according to claim 1 and 2, it is characterized in that described expanding material by in γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-amino propyl trimethoxy silicane, vinyl trimethylsilane, the methyl tri-tert peroxy-silane one or more by any than the mixture of forming.
8. a kind of high temperature resistant bimaleimide resin carrier structure glued membrane according to claim 1 and 2 is characterized in that described thixotropic agent is by aerosil, organobentonite or asbestos powder.
9. a kind of high temperature resistant bimaleimide resin carrier structure glued membrane according to claim 1 and 2 is characterized in that described carrier is by glass fiber woven cloth, silica fibrage cloth or carbon fiber woven cloth.
10. the preparation method of a high temperature resistant bimaleimide resin carrier structure glued membrane is characterized in that described high temperature resistant bimaleimide resin carrier structure glue film manufacturing process is to carry out according to following steps: the thixotropic agent that, takes by weighing 75～100 parts bimaleimide resin, 50～75 parts process modification agent, 10～20 parts of plasticized modifiers, 1～4 part of expanding material and 1～4 part by mass fraction; Two, the bimaleimide resin that step 1 is taken by weighing and process modification agent obtain copolymerization modification bismaleimide resin after joining in the reactor under whipped state heat temperature raising to 135～145 ℃ and being incubated 20～30 minutes; Three, the expanding material that step 1 is taken by weighing is dissolved in dehydrated alcohol to make solid content is 5% ethanolic soln, add the toughner that step 1 takes by weighing then, disperseed 5～10 minutes with 800～1000 rev/mins stir speed (S.S.) again, remove dehydrated alcohol and oven dry then, get the toughner after the processing; Four, adopt the mechanical blending method to mix the toughner of handling in the copolymerization modification bismaleimide resin that makes in the step 2 and the step 3, and then add the thixotropic agent that step 1 takes by weighing and continue to be blended into evenly, both obtained sizing material; Five, adopting three rollers to change under the auxiliary filming condition of carrier above-mentioned sizing material is coated with the film-making machine film forming, namely finishes the preparation of high temperature resistant bimaleimide resin carrier structure glued membrane; Wherein, described film-forming temperature is 70～90 ℃; The equipment of the described employing mechanical blending of step 4 is three-roll grinder or vacuum kneader; Described bimaleimide resin is to be that the ratio of 5:3:2 is formed by the high temperature resistant short chain bimaleimide resin of BMT type, 4,4 '-two amido ditane type bimaleimide resins and ether-containing key 44DADPE type bismaleimides in mass ratio.
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