CN103242767B - 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 glueing joint for load bearing structure, and it can transmit larger 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, membrane structure sizing agent because of have bondline thickness evenly controlled, the advantage such as fugitive constituent is low, high strength, high tenacity, high-durability and high reliability obtained and be widely used at aerospace field.
Because pure bimaleimide resin cured product cross-linking density is large, though temperature tolerance is high, but processing performance and toughness are poor, self neither possess filming condition and also cannot meet the toughness reguirements of structural film adhesive, therefore it is carried out to film-forming process modification and toughening modifying is gordian technique.Existing bimaleimide resin structural film adhesive generally adopts allyl group dihydroxyphenyl propane to 4, 4 '-bis-amido ditane type bimaleimide resins (BDM type bimaleimide resin) carry out copolymerization modification and improve its processing performance, then adopt second-phase (thermosetting resin, thermoplastic resin or rubber) it is carried out to outer toughening modifying, by solidification process be separated produce two phase structure reach toughening effect, be subject to toughner molecular weight, curing process and curing reaction Kinetics impact, be separated often not thorough, therefore the thermotolerance of sizing agent and modulus decline larger, toughness reinforcing reliability is also subject to certain impact.
At present, existing commercial bismaleimide structure glued membrane both at home and abroad, but all do not have high temperature resistant and high tenacity characteristic concurrently, as the second-order transition temperature of the ReduxHP655 span glued membrane of Hexcel company has reached 297.4 DEG C, but honeycomb sandwich construction climbing drum peel strength is only 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 DEG C, but honeycomb sandwich construction climbing drum peel strength is 20.2N.m/m(aluminum alloy outer cover/aluminium honeycomb), kind of the domestic Jin You J-188 of Institute of Petrochemistry, HLJ Academy of Science span glued membrane, its second-order transition temperature is only 210 DEG C of left and right, life-time service temperature is below 200 DEG C, and honeycomb sandwich construction climbing drum peel strength (aluminum alloy outer cover/aluminium honeycomb) is 35.0N.m/m.
Summary of the invention
The object of the invention is not have high-temperature resistant grade and high tenacity concurrently in order to solve existing bismaleimides glued membrane, and the poor problem that cannot big area paving of processing performance.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 up of thixotropic agent and the carrier of the bimaleimide resin of 75～100 parts, the process modification agent of 50～75 parts, the plasticized modifier of 10～25 parts, 1～4 part of expanding material and 1～4 part according to mass fraction; Wherein, described bimaleimide resin is to be the ratio composition of 5:3:2 in mass ratio by the high temperature resistant short chain bimaleimide resin of BMT type, 4,4 '-bis-amido ditane type bimaleimide resins and ether-containing key 44DADPE type bismaleimides.
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 the bimaleimide resin of 75～100 parts, the process modification agent of 50～75 parts, 10～20 parts of plasticized modifiers, 1～4 part of expanding material and 1～4 part by mass fraction; Two, bimaleimide resin step 1 being taken and process modification agent join in reactor, under whipped state, be heated to 135～145 DEG C and be incubated 20～30 minutes after obtain copolymerization modification bismaleimide resin; Three, expanding material step 1 being taken is dissolved in dehydrated alcohol, and to make solid content be 5% ethanolic soln, then the toughner that adds step 1 to take, disperse 5～10 minutes with the stir speed (S.S.) of 800～1000 revs/min again, then remove dehydrated alcohol and dry, obtain toughner after treatment; Four, adopt mechanical blending method to mix the toughner of processing in the copolymerization modification bismaleimide resin making in step 2 and step 3, and then add the thixotropic agent that step 1 takes to continue to be blended into evenly, both obtained sizing material; Five, under the auxiliary filming condition of carrier, adopting three rollers to turn above-mentioned sizing material is coated with film-making machine film forming, completes the preparation of high temperature resistant bimaleimide resin carrier structure glued membrane; Wherein, described film-forming temperature is 70～90 DEG C; The equipment of the employing mechanical blending described in step 4 is three-roll grinder or vacuum kneader; Described bimaleimide resin is to be the ratio composition of 5:3:2 in mass ratio by the high temperature resistant short chain bimaleimide resin of BMT type, 4,4 '-bis-amido ditane type bimaleimide resins and ether-containing key 44DADPE type bismaleimides.
The present invention comprises following beneficial effect:
The present invention adopts the bismaleimide resin mixture of different structure feature as matrix resin, adopting heat resist modification agent is process modification material, (adopt expanding material to its surface treatment) taking inorganic and organic compound as toughner, taking inorganic nano-filler as thixotropic agent, taking fibrous braid as carrier, adopt copolymerization, mechanical blending technology is prepared 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 reliability high, processing performance good etc. feature, can meet with bismaleimide resin based composites big area co-curing and glued joint requirement, be expected to obtain application in the manufacture of aerospace field refractory metal or composite material structural member.
1, it is matrix resin that the present invention has adopted three kinds of bismaleimide resin monomers, wherein taking high temperature resistant short chain bismaleimide resin (BMT) as main body, introducing portion 4, the bimaleimide resin (44DADPE) of 4 '-bis-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 feature preferably, combine and adopted allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane are as process modification agent, the modification bismaleimide resin making has high temperature resistant and feature good manufacturability, the second-order transition temperature of sizing agent has reached 280 DEG C of left and right, resin can soften melting film forming at 60～100 DEG C, and sizing agent processing performance is good,
2, to adopt the inorganic and organic toughner of associating to carry out sizing agent toughness reinforcing in the present invention, and adopt expanding material to process to its surface, increases it and be combined and cohesive strength with the interface of interlaminar resin.Adopt the advantage of the inorganic toughness reinforcing sizing agents such as super fiber, inorganic salt whisker and nanometer powder to be: it has toughness reinforcing and enhancement concurrently to sizing agent, this point is that organic toughner is incomparable, there is certain contribution to improving second-order transition temperature, make the sizing agent second-order transition temperature of the present invention can be up to 280 DEG C of left and right.The present invention is different from the toughening technology that other polymer toughening sizing agents are separated, the ultrafine powder that the homogeneous system that adopts second-order transition temperature to differ larger two kinds of thermoplastic resins is prepared through pulverize at low temperature is carried out toughness reinforcing to sizing agent, as toughness reinforcing in the ultrafine powder that adopts polyetherimide and two kinds of thermoplastic resins of polyamidoimide to prepare, the second-order transition temperature that polyetherimide is lower on the one hand can mutually fuse the stronger interface cohesive force of formation with modification bismaleimide resin system in sizing agent heats up curing engineering, play good compatibilization, polyamidoimide in homogeneous system does not occur to change mutually because having higher glass transition temperature on the other hand, this island structure with Interfacial compatibilization is the basis that sizing agent of the present invention obtains higher toughness, greatly improve the toughness of sizing agent.Combine organic and inorganic toughner and sizing agent is given tough, make it have high-temperature resistant grade and high tenacity feature concurrently, its second-order transition temperature has reached 280 DEG C of left and right, and (glued membrane area density is 244g/m to sizing agent
2)-55 DEG C of shearing resistances reached about 15.0MPa; More than normal temperature shearing resistance has reached 18.0MPa, 260 DEG C have reached 15.0MPa, still keep 13.0 left and right at 288 DEG C, and in 5.0MPa left and right, (glued membrane area density is 390g/m to sizing agent at 316 DEG C
2) glued joint aluminium honeycomb sandwich construction climbing drum peel strength and reached 75N.m/m, ((glued membrane area density is 390g/m to sizing agent
2)) glued joint more than aluminium honeycomb planar stretch intensity reached 5.0MPa.
Brief description of the drawings
Fig. 1 is the DSC graphic representation of the test 1 high temperature resistant bimaleimide resin carrier structure glued membrane making.
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 up of thixotropic agent and the carrier of the bimaleimide resin of 75～100 parts, the process modification agent of 50～75 parts, the plasticized modifier of 10～25 parts, 1～4 part of expanding material and 1～4 part according to mass fraction; Wherein, described bimaleimide resin is to be the ratio composition of 5:3:2 in mass ratio by the high temperature resistant short chain bimaleimide resin of BMT type, 4,4 '-bis-amido ditane type bimaleimide resins and ether-containing key 44DADPE type bismaleimides.
The BMT type bimaleimide resin of present embodiment is commercially available prod, and its chemical structural formula is as follows,
The 44DADPE type bimaleimide resin of present embodiment is according to (Zhu Yulong, Yu Xinhai. synthesizing of novel ether-linked bismaleimides, 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 feature as matrix resin, adopting high temperature resistant copolymerization properties-correcting agent is process modification material, (adopt expanding material to its surface treatment) taking inorganic and organic compound as toughner, taking inorganic nano-filler as thixotropic agent, taking fibrous braid as carrier, adopt prepolymerization, mechanical blending technology is prepared 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 reliability high, processing performance good etc. feature, can meet with bismaleimide resin based composites big area co-curing and glued joint requirement, be expected to obtain application in the manufacture of aerospace field refractory metal or composite material structural member.
1, it is matrix resin that present embodiment has adopted three kinds of bismaleimide resin monomers, wherein taking high temperature resistant short chain bismaleimide resin (BMT) as main body, introducing portion 4, the bimaleimide resin (44DADPE) of 4 '-bis-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 feature preferably, combine and adopted allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane are as properties-correcting agent, the modification bismaleimide resin making has high temperature resistant and feature good manufacturability, the second-order transition temperature of sizing agent has reached more than 280 DEG C, resin can soften melting film forming at 60～100 DEG C, and sizing agent processing performance is good,
2, to adopt the inorganic and organic toughner of associating to carry out sizing agent toughness reinforcing for present embodiment, and adopt expanding material to process to its surface, increases it and be combined and cohesive strength with the interface of interlaminar resin.Adopt the advantage of the inorganic toughness reinforcing sizing agents such as super fiber, inorganic salt whisker and nanometer powder to be: it has toughness reinforcing and enhancement concurrently to sizing agent, this point is that organic toughner is incomparable, there is certain contribution to improving second-order transition temperature, make the present embodiment sizing agent second-order transition temperature can be up to more than 280 DEG C.Present embodiment is different from the toughening technology that other polymer toughening sizing agents are separated, the ultrafine powder that the homogeneous system that adopts second-order transition temperature to differ larger two kinds of thermoplastic resins is prepared through pulverize at low temperature is carried out toughness reinforcing to sizing agent, as toughness reinforcing in the ultrafine powder that adopts polyetherimide and two kinds of thermoplastic resins of polyamidoimide to prepare, the second-order transition temperature that polyetherimide is lower on the one hand can mutually fuse the stronger interface cohesive force of formation with modification bismaleimide resin system in sizing agent heats up curing engineering, play good compatibilization, polyamidoimide in homogeneous system does not occur to change mutually because having higher glass transition temperature on the other hand, this island structure with Interfacial compatibilization is the basis that present embodiment sizing agent obtains higher thermal toughness, greatly improve the toughness of sizing agent.Combine organic and inorganic toughner and sizing agent is given tough, make it have high-temperature resistant grade and high tenacity feature concurrently, its second-order transition temperature has reached more than 280 DEG C, and (glued membrane area density is 244g/m to sizing agent
2)-55 DEG C of shearing resistances reached about 15.0MPa; More than normal temperature shearing resistance has reached 18.0MPa, 260 DEG C have reached 15.0MPa, still keep 13.0 left and right at 288 DEG C, and in 5.0MPa left and right, (glued membrane area density is 390g/m to sizing agent at 316 DEG C
2) glued joint aluminium honeycomb sandwich construction climbing drum peel strength and reached 75.0N.m/m, ((glued membrane area density is 390g/m to sizing agent
2)) glued joint more than aluminium honeycomb planar stretch intensity reached 5.0MPa.
Embodiment two: present embodiment is different from embodiment one: described high temperature resistant bimaleimide resin carrier structure glued membrane is to be made up of the bimaleimide resin of 80～90 parts, 55～70 parts of process modification agent, the plasticized modifier of 15～20 parts, the expanding material of 2～4 parts and thixotropic agent and the carrier of 2～4 parts according to mass fraction.Other are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: 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: present embodiment is different from one of embodiment one to three: 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.Other steps and parameter are identical with one of embodiment one to three.
Embodiment five: what present embodiment was different from one of embodiment one to four is that described inorganic toughner is one or more mixtures that form by any ratio in super fiber, inorganic salt whisker, inorganic nano powder; Wherein super fiber is single wall or multi-walled carbon nano-tubes, inorganic salt whisker is one or more mixtures that form by any ratio in silicon carbide whisker, aluminium borate whisker or calcium sulfate crystal whiskers, and inorganic nano powder is one or more mixtures that form by any ratio of silica powder, aluminium sesquioxide and titanium dioxide.Other steps and parameter are identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five: described organic toughner is prepared as follows: polyetherimide and polyamidoimide, phenolphthalein base polyaryletherketone and polyamidoimide or polyethersulfone with cardo and polyamidoimide are dissolved in and form desolvation after homogeneous system in trichloromethane solvent, then adopt Lowtemperaturepulverizer using its pulverizing 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; Polyethersulfone with cardo and polyamidoimide are 1:3～4 in mass ratio.Other steps and parameter are identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six: described expanding material by one or more in γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-amino propyl trimethoxy silicane, vinyl trimethylsilane, methyl tri-tert peroxy-silane by arbitrarily than the mixture forming.Other steps and parameter are identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven: described thixotropic agent is by aerosil, organobentonite or asbestos powder.Other steps and parameter are identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight: described carrier is by glass fiber woven cloth, silica fibrage cloth or carbon fiber woven cloth.Other steps and parameter are identical with one of embodiment one to eight.
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 the bimaleimide resin of 75～100 parts, the process modification agent of 50～75 parts, 10～20 parts of plasticized modifiers, 1～4 part of expanding material and 1～4 part by mass fraction; Two, bimaleimide resin step 1 being taken and process modification agent join in reactor, under whipped state, be heated to 135～145 DEG C and be incubated 20～30 minutes after obtain copolymerization modification bismaleimide resin; Three, expanding material step 1 being taken is dissolved in dehydrated alcohol, and to make solid content be 5% ethanolic soln, then the toughner that adds step 1 to take, disperse 5～10 minutes with the stir speed (S.S.) of 800～1000 revs/min again, then remove dehydrated alcohol and dry, obtain toughner after treatment; Four, adopt mechanical blending method to mix the toughner of processing in the copolymerization modification bismaleimide resin making in step 2 and step 3, and then add the thixotropic agent that step 1 takes to continue to be blended into evenly, both obtained sizing material; Five, under the auxiliary filming condition of carrier, adopting three rollers to turn above-mentioned sizing material is coated with film-making machine film forming, completes the preparation of high temperature resistant bimaleimide resin carrier structure glued membrane; Wherein, described film-forming temperature is 70～90 DEG C; The equipment of the employing mechanical blending described in step 4 is three-roll grinder or vacuum kneader; Described bimaleimide resin is to be the ratio composition of 5:3:2 in mass ratio by the high temperature resistant short chain bimaleimide resin of BMT type, 4,4 '-bis-amido ditane type bimaleimide resins and ether-containing key 44DADPE type bismaleimides.
The BMT type bimaleimide resin of present embodiment is commercially available prod, and its chemical structural formula is as follows,
The 44DADPE type bimaleimide resin of present embodiment is according to disclosed method (Zhu Yulong, Yu Xinhai. synthesizing of novel ether-linked bismaleimides, 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 feature as matrix resin, adopting high temperature resistant copolymerization properties-correcting agent is process modification material, (adopt expanding material to its surface treatment) taking inorganic and organic compound as toughner, taking inorganic nano-filler as thixotropic agent, taking fibrous braid as carrier, adopt copolymerization, mechanical blending technology is prepared 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 reliability high, processing performance good etc. feature, can meet with bismaleimide resin based composites big area co-curing and glued joint requirement, be expected to obtain application in the manufacture of aerospace field refractory metal or composite material structural member.
1, it is matrix resin that present embodiment has adopted three kinds of bismaleimide resin monomers, wherein taking high temperature resistant short chain bismaleimide resin (BMT) as main body, introducing portion 4, the bimaleimide resin (44DADPE) of 4 '-bis-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 feature preferably, combine and adopted allyl ethers resol, allyl group dihydroxyphenyl propane and hyperbranched polyorganosiloxane are as properties-correcting agent, the copolymerization modification bismaleimide resin making has high temperature resistant and feature good manufacturability, the second-order transition temperature of sizing agent has reached more than 280 DEG C, resin can soften melting film forming at 60～100 DEG C, and sizing agent processing performance is good,
2, to adopt the inorganic and organic toughner of associating to carry out sizing agent toughness reinforcing for present embodiment, and adopt expanding material to process to its surface, increases it and be combined and cohesive strength with the interface of interlaminar resin.Adopt the advantage of the inorganic toughness reinforcing sizing agents such as super fiber, inorganic salt whisker and nanometer powder to be: it has toughness reinforcing and enhancement concurrently to sizing agent, this point is that organic toughner is incomparable, there is certain contribution to improving second-order transition temperature, make the present embodiment sizing agent second-order transition temperature can be up to more than 280 DEG C.Present embodiment is different from the toughening technology that other polymer toughening sizing agents are separated, the ultrafine powder that the homogeneous system that adopts second-order transition temperature to differ larger two kinds of thermoplastic resins is prepared through pulverize at low temperature is carried out toughness reinforcing to sizing agent, as toughness reinforcing in the ultrafine powder that adopts polyetherimide and two kinds of thermoplastic resins of polyamidoimide to prepare, the second-order transition temperature that polyetherimide is lower on the one hand can mutually fuse the stronger interface cohesive force of formation with modification bismaleimide resin system in sizing agent heats up curing engineering, play good compatibilization, polyamidoimide in homogeneous system does not occur to change mutually because having higher glass transition temperature on the other hand, this island structure with Interfacial compatibilization is the basis that present embodiment sizing agent obtains higher thermal toughness, greatly improve the toughness of sizing agent.Combine organic and inorganic toughner and sizing agent is given tough, make it have high-temperature resistant grade and high tenacity feature concurrently, its second-order transition temperature has reached more than 280 DEG C, and (glued membrane area density is 244g/m to sizing agent
2)-55 DEG C of shearing resistances reached about 15.0MPa; More than normal temperature shearing resistance has reached 18.0MPa, 260 DEG C have reached 15.0MPa, still keep 13.0 left and right at 288 DEG C, and in 5.0MPa left and right, (glued membrane area density is 390g/m to sizing agent at 316 DEG C
2) glued joint aluminium honeycomb sandwich construction climbing drum peel strength and reached 75.0N.m/m, ((glued membrane area density is 390g/m to sizing agent
2)) glued joint more than aluminium honeycomb planar stretch intensity reached 5.0MPa.
Embodiment 11: present embodiment is different from embodiment ten: 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 and parameter are identical with embodiment ten.
Embodiment 12: present embodiment is different from embodiment ten or 11: 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.
Other steps and parameter are identical with embodiment ten or 11.
Embodiment 13: present embodiment is different from one of embodiment ten to 12: described inorganic toughner is one or more mixtures that form by any ratio in super fiber, inorganic salt whisker, inorganic nano powder; Wherein super fiber is single wall or multi-walled carbon nano-tubes, inorganic salt whisker is one or more mixtures that form by any ratio in silicon carbide whisker, aluminium borate whisker or calcium sulfate crystal whiskers, and inorganic nano powder is one or more mixtures that form by any ratio of silica powder, aluminium sesquioxide and titanium dioxide.Other steps and parameter are identical with one of embodiment ten to 12.
Embodiment 14: present embodiment is different from one of embodiment ten to 13: described organic toughner is prepared as follows: polyetherimide and polyamidoimide, phenolphthalein base polyaryletherketone and polyamidoimide or polyethersulfone with cardo and polyamidoimide are dissolved in and form desolvation after homogeneous system in trichloromethane solvent, then adopt Lowtemperaturepulverizer using its pulverizing 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; Polyethersulfone with cardo and polyamidoimide are 1:3～4 in mass ratio.Other steps and parameter are identical with one of embodiment ten to 13.
Embodiment 15: present embodiment is different from one of embodiment ten to 14: described expanding material by one or more in γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-amino propyl trimethoxy silicane, vinyl trimethylsilane, methyl tri-tert peroxy-silane by arbitrarily than the mixture forming.Other steps and parameter are identical with one of embodiment ten to 14.
Embodiment 16: present embodiment is different from one of embodiment ten to 15: described thixotropic agent is by aerosil, organobentonite or asbestos powder.Other steps and parameter are identical with one of embodiment ten to 15.
Embodiment 17: present embodiment is different from one of embodiment ten to 16: described carrier is by glass fiber woven cloth, silica fibrage cloth or carbon fiber woven cloth.Other steps and parameter are identical with one of embodiment ten to 16.
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 the bimaleimide resin of 100 parts, the process modification agent of 75 parts, 20 parts of plasticized modifiers, 3 parts of expanding materials and 3 parts by mass fraction; Two, bimaleimide resin step 1 being taken and process modification agent join in reactor, under whipped state, be heated to 140 DEG C and be incubated 25 minutes after obtain copolymerization modification bismaleimide resin; Three, expanding material step 1 being taken is dissolved in dehydrated alcohol, and to make solid content be 5% ethanolic soln, then the toughner that adds step 1 to take, stir 6 minutes with the speed of 900 revs/min again, then remove dehydrated alcohol and dry, obtain toughner after treatment; Four, adopt mechanical blending method to mix the toughner of processing in the copolymerization modification bismaleimide resin making in step 2 and step 3, and then add the thixotropic agent that step 1 takes to continue to be blended into evenly, both obtained sizing material; Five, under the auxiliary filming condition of carrier, adopting three rollers to turn above-mentioned sizing material is coated with film forming on film-making machine, completes the preparation of high temperature resistant bimaleimide resin carrier structure glued membrane; Wherein, described film-forming temperature is 80 DEG C; The equipment of the employing mechanical blending described in 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 composition of 4 '-bis-amido ditane type bimaleimide resins (BDM) and 44DADPE type ether-containing key, and three's consumption is counted the high temperature resistant short chain bimaleimide resin of BMT type in mass ratio: the bismaleimide resin=5:3:2 of BDM:44DADPE type ether-containing key;
Described plasticized modifier by inorganic and organic toughner in mass ratio 1:5 form, 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 is prepared as follows: polyetherimide and polyamidoimide are formed to desolvation after homogeneous system for 1:4.5 is dissolved in mass ratio in trichloromethane methane, then adopt low-temperature airflow pulverizer using 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 steamed bun peak, reacting initial temperature is about 172.3 DEG C, reaction summit temperature is 247.6 DEG C, reaction end temp is at 334.7 DEG C, solidification range is wider, can match with bismaleimide resin based composites curing process window, and can meet two kinds of co-curing techniques: 1. stop 1 hour at 125 DEG C, at 175 DEG C, solidify 4 hours+200 DEG C and solidify 1 hour, 230 DEG C of aftertreatments 4 hours; 2. stop 1 hour at 125 DEG C, solidify 4 hours at 175 DEG C, 200 DEG C solidify 1 hour, aftertreatment 4 hours at 1 hour+260 DEG C of aftertreatments at 230 DEG C.This test adopts the former curing process.
High tenacity bimaleimide resin carrier structure glued membrane to this test preparation carries out the test of mechanical property, and test adopts titanium alloy test piece.Test result: the second-order transition temperature of sizing agent cured product has reached 283.6 DEG C, (glued membrane area density is 244g/m to sizing agent
2)-55 DEG C of shearing resistances reached about 15.4MPa; More than normal temperature shearing resistance has reached 19.6MPa, 260 DEG C have reached 14.8MPa, still keep 13.4 left and right at 288 DEG C, and in 4.9MPa left and right, (glued membrane area density is 390g/m to sizing agent at 316 DEG C
2) glued joint aluminium honeycomb sandwich construction climbing drum peel strength and reached 78.1N.m/m, ((glued membrane area density is 390g/m to sizing agent
2)) glued joint more than aluminium honeycomb planar stretch intensity reached 4.2MPa.
Testing method: GJB1709-1993 tackiness agent cryogenic tensile shearing resistance measuring method; The mensuration of GB/T7124-2008 tackiness agent tensile shear 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 the bimaleimide resin of 90 parts, the process modification agent of 70 parts, 15 parts of plasticized modifiers, 2 parts of expanding materials and 3 parts by mass fraction; Two, bimaleimide resin step 1 being taken and process modification agent join in reactor, under whipped state, be heated to 145 DEG C and be incubated 20 minutes after obtain copolymerization modification bismaleimide resin; Three, expanding material step 1 being taken is dissolved in dehydrated alcohol, and to make solid content be 5% ethanolic soln, then the toughner that adds step 1 to take, stir 8 minutes with the speed of 1000 revs/min again, then remove dehydrated alcohol and dry, obtain toughner after treatment; Four, adopt mechanical blending method to mix the toughner of processing in the copolymerization modification bismaleimide resin making in step 2 and step 3, and then add the thixotropic agent that step 1 takes to continue to be blended into evenly, both obtained sizing material; Five, under the auxiliary filming condition of carrier, adopting three rollers to turn above-mentioned sizing material is coated with film forming on film-making machine, completes the preparation of high temperature resistant bimaleimide resin carrier structure glued membrane; Wherein, described film-forming temperature is 75 DEG C; The equipment of the employing mechanical blending described in 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 composition of 4 '-bis-amido ditane type bimaleimide resins (BDM) and 44DADPE type ether-containing key, and three's the consumption high temperature resistant short chain bimaleimide resin of BMT type in mass ratio: the bismaleimide resin=5:3:2 of BDM:44DADPE type ether-containing key;
Described plasticized modifier by inorganic and organic toughner in mass ratio 1:5 form, wherein inorganic toughner is that silicon carbide whisker and titanium dioxide are the ratio composition of 1:1 in mass ratio, organic toughner is prepared as follows: polyethersulfone with cardo and polyamidoimide are formed to desolvation after homogeneous system for 1:3.5 is dissolved in mass ratio in trichloromethane methane, then adopt low-temperature airflow pulverizer using 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: stop at 125 DEG C 1 hour, solidify 4 hours at 175 DEG C, 200 DEG C solidify 1 hour, aftertreatment 4 hours at 1 hour+260 DEG C of aftertreatments at 230 DEG C.Test material preparation is undertaken by BMS5-154E specification, and the two lap shear test of tackiness agent are undertaken by BSS7202 method.
Test result: the high tenacity bimaleimide resin carrier structure glued membrane-55 DEG C down cut intensity of this test preparation has reached 15.0MPa, normal temperature shearing resistance can reach 18.7MPa, 260 DEG C of shearing resistances can reach 14.2MPa, and 288 DEG C of shearing resistances have reached 12.5MPa.
Claims (5)
1. a 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 up of thixotropic agent and the carrier of the bimaleimide resin of 75～100 parts, the process modification agent of 50～75 parts, the plasticized modifier of 10～25 parts, 1～4 part of expanding material and 1～4 part according to mass fraction;
Wherein, described bimaleimide resin is to be the ratio composition of 5:3:2 in mass ratio by the high temperature resistant short chain bimaleimide resin of BMT type, 4,4 '-bis-amido ditane type bimaleimide resins and ether-containing key 44DADPE type bismaleimides;
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;
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;
Described inorganic toughner is one or more mixtures that form by any ratio in super fiber, inorganic salt whisker, inorganic nano powder; Wherein super fiber is single wall or multi-walled carbon nano-tubes, inorganic salt whisker is one or more mixtures that form by any ratio in silicon carbide whisker, aluminium borate whisker or calcium sulfate crystal whiskers, and inorganic nano powder is one or more mixtures that form by any ratio of silica powder, aluminium sesquioxide and titanium dioxide;
Described organic toughner is prepared as follows: polyetherimide and polyamidoimide, phenolphthalein base polyaryletherketone and polyamidoimide or polyethersulfone with cardo and polyamidoimide are dissolved in and in trichloromethane solvent, form desolvation after homogeneous system, then adopt Lowtemperaturepulverizer using its pulverizing 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; Polyethersulfone with cardo and polyamidoimide are 1:3～4 in mass ratio;
Described expanding material by one or more in γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-amino propyl trimethoxy silicane, vinyl trimethylsilane, methyl tri-tert peroxy-silane by arbitrarily than the mixture forming.
2. the high temperature resistant bimaleimide resin carrier structure of one according to claim 1 glued membrane, is characterized in that described high temperature resistant bimaleimide resin carrier structure glued membrane is to be made up of the bimaleimide resin of 80～90 parts, 55～70 parts of process modification agent, the plasticized modifier of 15～20 parts, the expanding material of 2～4 parts and thixotropic agent and the carrier of 2～4 parts according to mass fraction.
3. the high temperature resistant bimaleimide resin carrier structure of one according to claim 1 and 2 glued membrane, is characterized in that described thixotropic agent is by aerosil, organobentonite or asbestos powder.
4. the high temperature resistant bimaleimide resin carrier structure of one according to claim 1 and 2 glued membrane, is characterized in that described carrier is by glass fiber woven cloth, silica fibrage cloth or carbon fiber woven cloth.
5. a preparation method for high temperature resistant bimaleimide resin carrier structure glued membrane as claimed in claim 1, 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 the bimaleimide resin of 75～100 parts, the process modification agent of 50～75 parts, 10～20 parts of plasticized modifiers, 1～4 part of expanding material and 1～4 part by mass fraction; Two, bimaleimide resin step 1 being taken and process modification agent join in reactor, under whipped state, be heated to 135～145 DEG C and be incubated 20～30 minutes after obtain copolymerization modified bismaleimide resin; Three, expanding material step 1 being taken is dissolved in dehydrated alcohol, and to make solid content be 5% ethanolic soln, then the plasticized modifier that adds step 1 to take, disperse 5～10 minutes with the stir speed (S.S.) of 800～1000 revs/min again, then remove dehydrated alcohol and dry, obtaining plasticized modifier after treatment; Four, adopt mechanical blending method to mix the plasticized modifier of processing in the copolymerization modified bismaleimide resin making in step 2 and step 3, and then add the thixotropic agent that step 1 takes to continue to be blended into evenly, both obtained sizing material; Five, under the auxiliary filming condition of carrier, adopting three rollers to turn above-mentioned sizing material is coated with film-making machine film forming, completes the preparation of high temperature resistant bimaleimide resin carrier structure glued membrane; Wherein, described film-forming temperature is 70～90 DEG C; The equipment of the employing mechanical blending described in step 4 is three-roll grinder or vacuum kneader; Described bimaleimide resin is to be the ratio composition of 5:3:2 in mass ratio by the high temperature resistant short chain bimaleimide resin of BMT type, 4,4 '-bis-amido ditane type bimaleimide resins and ether-containing key 44DADPE type bismaleimides.
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| CN109851970B (en) * | 2019-02-10 | 2021-02-09 | 江苏宇豪新材料科技有限公司 | High-toughness bismaleimide resin material and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263901A (en) * | 2000-03-14 | 2000-08-23 | 复旦大学 | Polyetherimide modified bimalieimide resin |
| CN101531880A (en) * | 2009-04-28 | 2009-09-16 | 黑龙江省科学院石油化学研究院 | Canate-bimaleimide resin adhesive and preparation method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03290489A (en) * | 1990-04-09 | 1991-12-20 | Sumitomo Bakelite Co Ltd | Imide adhesive |
| US6960636B2 (en) * | 1994-09-02 | 2005-11-01 | Henkel Corporation | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
-
2013
- 2013-05-20 CN CN201310187697.3A patent/CN103242767B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263901A (en) * | 2000-03-14 | 2000-08-23 | 复旦大学 | Polyetherimide modified bimalieimide resin |
| CN101531880A (en) * | 2009-04-28 | 2009-09-16 | 黑龙江省科学院石油化学研究院 | Canate-bimaleimide resin adhesive and preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694454A (en) * | 2016-03-24 | 2016-06-22 | 湖州新奥克化工有限公司 | BMI resin-base composite material and preparation method thereof |
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