CN105418923A - Modified bismaleimide resin and preparation method thereof - Google Patents

Modified bismaleimide resin and preparation method thereof Download PDF

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CN105418923A
CN105418923A CN201610043318.7A CN201610043318A CN105418923A CN 105418923 A CN105418923 A CN 105418923A CN 201610043318 A CN201610043318 A CN 201610043318A CN 105418923 A CN105418923 A CN 105418923A
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bismaleimide resin
modified bismaleimide
preparation
resin
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CN105418923B (en
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梁国正
韩贤超
顾嫒娟
袁莉
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Suzhou University
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Suzhou University
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses modified bismaleimide resin and a preparation method of the modified bismaleimide resin. The preparation method comprises the steps of dissolving a 2-aminoterephthalic acid in N,N-dimethyl formamide, carrying out activating treatment by using alcohol after a reaction is carried out by adding AlCl3.6H2O, and obtaining an amination metal organic framework; then mixing the amination metal organic framework with a diallyl phenyl compound, adding bismaleimide, and obtaining the modified bismaleimide resin through solidification and after-treatment. According to the modified bismaleimide resin disclosed by the invention, the amination metal organic framework is small in duct size and low in specific surface area, a cavity structure is enabled to be reserved in the modified bismaleimide resin, and low-dielectric constants are facilitated to be obtained; good moisture resistance and good mechanical property of the modified bismaleimide resin are ensured; meanwhile, the metal organic framework carries aminos, hydroxyls and carboxyls and has a good reactivity and a good physical interaction with bismaleimide, a good dispersing and interface force is obtained by the metal organic framework in resin, the polarity density in cured resin is reduced, and the dielectric loss is facilitated to be reduced.

Description

A kind of modified bismaleimide resin and preparation method thereof
Technical field
The present invention relates to a kind of thermosetting resin and preparation method thereof, particularly a kind of modified bismaleimide resin and preparation method thereof, belong to high-performance polymer technical field.
Background technology
Along with the develop rapidly of microelectronic industry art of new generation, the demand of performance resins is increased day by day, except the requirement of high heat resistance, high tenacity, more requirement is proposed to low-k, low-dielectric loss.Bismaleimides (BMI) resin is one of Typical Representative of heat-resisting thermosetting resin, but its toughness and dielectric properties remain to be further improved.
Method generally by reducing molecular polarity density reduces the specific inductivity of polymkeric substance.Specific inductivity due to air is 1, and therefore introducing porous material or pore-creating agent is in the polymer prepare the simple and effective means of of advanced low-k materials.
So far, investigators respectively using materials such as cyclodextrin, mesoporous silicon (SBA-15) and silsesquioxanes (POSS) as pore-creating agent, join in resin and prepare low-k resin.But, these pore-creating agents not easily effectively disperse in organic matrix, therefore, usual needs introduce more active group on surface, but, the introducing of these active groups usually increases the polarity of resin, and partial offset reduces effect of specific inductivity, to be also usually not easy to obtain low-dielectric loss simultaneously.In addition, if when the volume fraction of matrix mesopore is more than 30%, hole is tended to mutually run through, and causes material be easy to moisture absorption and specific inductivity is raised; Meanwhile, too much hole also can be easy to form crackle, reduces the mechanical property of material.Therefore, the structure designing suitable pore-creating agent is most important when preparing novel high-performance resin.
Rigid inorganic filler toughening is one of toughness reinforcing method of thermosetting resin.It is toughness reinforcing that people once utilized inorganic mesoporous material to carry out.Such as, the people such as Jiao are (see document: JiaoJ, WangL, LvP, etal.Improveddielectricandmechanicalpropertiesofsilica/e poxyresinnanocompositespreparedwithanovelorganic – inorganichybridmesoporoussilica:POSS – MPS [J] .MaterialsLetters, 2014,129:16-19) prepare a kind of POSS(POSS-MPS of mesoporous silicon oxide functionalization), and for modified epoxy.When POSS-MPS content is 5.0wt%, flexural strength, the shock strength of rigid epoxy resin all increase significantly, though specific inductivity and loss have reduction, lowest dielectric constant and loss are still respectively 3.66 and 0.017, need further reduction.
Metallic organic framework (MOFs) is obtained by self assembling process between organic ligand and suitable metallic cation, there is open grain, high-ratio surface, selective adsorption, thermostability comparatively high, demonstrate tempting application prospect in various fields such as gas storage, gas adsorption separation, selectivity and chiral catalyst, microreactor, molecular recognition, drug delivery, photoelectric properties application.2014, Roy etc. took the lead in being introduced by MOF-5 in epoxy resin (EP), have prepared MOF-5/EP, have studied MOF-5 and added impact on resin mechanics (see document: RoyPK, RamananA.TougheningofepoxyresinusingZn 4o (Isosorbide-5-Nitrae-benzenedicarboxylate) 3metal – organicframeworks [J] .RSCAdvances, 2014,4 (94): 52338-52345).Find that adding 0.3wt%MOF-5 can make Izod notched impact strength, energy-to-break G icwith fracture toughness property K icimprove 68%, 30% and 36% respectively.But the work of dielectric properties aspect is not reported in this research; In addition, the MOF-5 used stability in wet environment is not good, sudden and violent leakage has just had the structure collapses of local (see document: JiangJ in 2 days in damp atmosphere, FengY, ChenM, etal.Synthesisandhydrogen-storageperformanceofinterpenet ratedMOF-5/MWCNTshybridcompositewithhighmesoporosity [J] .InternationalJournalofhydrogenEnergy, 2013,38 (25): 10950-10955).
In sum, prior art makes great progress in performance resins research and development, obtain the resin variety significantly improved in a certain performance, but, have concurrently the multinomial performances such as thermotolerance, toughness, dielectric properties in need perfect further.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, a kind of modified bismaleimide resin and preparation method thereof having low-k, low-dielectric loss, high tenacity, high rigidity, high heat resistance concurrently is provided.
For achieving the above object, the technical solution adopted in the present invention is: a kind of preparation method of modified bismaleimide resin, comprises following steps:
1, under nitrogen protection condition, by mol, amino for 0.4 ~ 0.7 part of 2-terephthalic acid is dissolved in 0.4 ~ 0.8 part of DMF, is under the condition of 110 ~ 150 DEG C in temperature, adds 1 part of AlCl 36H 2o, is stirred to dissolving, then insulation reaction 10 ~ 15 hours, after naturally cooling to room temperature, carries out filtering, washs, centrifugal treating, then is, under the condition of 85 ~ 90 DEG C, use Ethanol activation process, obtain metal amides organic backbone after drying in temperature;
2, the metal amides organic backbone that step 1 is obtained is mixed with diallyl phenyl compound, obtain mixture A;
3, being joined by bismaleimides in mixture A, is mix under the condition of 130 ~ 150 DEG C in temperature, through solidification and aftertreatment, obtains a kind of modified bismaleimide resin.
In technical solution of the present invention, described bismaleimides is N, N'-4, the one in 4 '-diphenyl methane dimaleimide, N, N'-4,4'-Diphenyl Ether Bismaleimide, or their arbitrary combination.Described diallyl phenyl compound is 2,2 '-diallyl bisphenol, 2, the one in 2 '-diallyl bisphenol S, or their arbitrary combination.
Preferred version of the present invention is: in molar ratio, and diallyl phenyl compound and bismaleimides are 0.7 ~ 1.0:1.In mass ratio, the quality sum of diallyl phenyl compound and bismaleimides and metallic organic framework are 100:0.1 ~ 1.0.
Technical solution of the present invention also comprises a kind of modified bismaleimide resin obtained by above-mentioned preparation method.
Compared with prior art, the beneficial effect that the present invention obtains is:
The pore size of the metal amides organic backbone 1, obtained by the present invention is little, and specific surface area is low, and this is that the size of microcrystal of metal amides organic backbone obtained by the present invention is little.This metal amides organic backbone makes molecular resin can not enter metallic organic framework duct, thus makes cavity structure be able to retain in resin, is conducive to obtaining low-k.And relatively low cavity structure ratio, also ensure that resin has good wet fastness and mechanical property simultaneously.
2, with amino, hydroxyl and carboxyl on the metal amides organic backbone obtained by the present invention, they and bismaleimides have good reactivity and Physical interaction, not only guarantee that metallic organic framework obtains good distribution and interface interaction power in resin, and the polarity density in reduction cured resin, contribute to reducing dielectric loss.The dielectric loss of the resin developed when 100Hz is only about 0.001.
3, the preparation method of modified bismaleimide resin provided by the invention have technique simple, be easy to control, the features such as raw material sources is wide.
Accompanying drawing explanation
Fig. 1 is powder x-ray diffraction spectrum (XRD) figure of the metallic organic framework of comparative example 1 of the present invention synthesis and the metal amides organic backbone of embodiment 1 synthesis.
Fig. 2 is infrared spectra (FTIR) figure of the metallic organic framework of comparative example 1 of the present invention synthesis and the metal amides organic backbone of embodiment 1 synthesis.
Fig. 3 is scanning electron microscope (SEM) and transmission electron microscope (TEM) photo of the metallic organic framework of comparative example 1 of the present invention synthesis and the metal amides organic backbone of embodiment 1 synthesis.
Fig. 4 is the isothermal adsorption desorption curve figure of the metal amides organic backbone that the embodiment of the present invention 1 is synthesized.
Fig. 5 is the specific inductivity-frequency curve of the bimaleimide resin that the modified bismaleimide resin that provides of the embodiment of the present invention 1,2 and comparative example 2 provide.
Fig. 6 is the dielectric loss-frequency curve of the bimaleimide resin that the modified bismaleimide resin that provides of the embodiment of the present invention 1,2 and comparative example 2 provide.
Fig. 7 is the shock strength of the bimaleimide resin that the modified bismaleimide resin that provides of the embodiment of the present invention 1,2 and comparative example 2 provide.
Fig. 8 is the flexural strength of the bimaleimide resin that the modified bismaleimide resin that provides of the embodiment of the present invention 1,2 and comparative example 2 provide.
Fig. 9 is the storage modulus-temperature curve of the bimaleimide resin that the modified bismaleimide resin that provides of the embodiment of the present invention 1,2 and comparative example 2 provide.
Embodiment
Below in conjunction with accompanying drawing, embodiment and comparative example, technical solution of the present invention is further described.
Embodiment 1
1, the preparation of metal amides organic backbone
Under nitrogen protection condition, amino for 0.272g2-terephthalic acid is dissolved in the DMF of 62mL; At temperature 110 DEG C and agitation condition, add 0.724gAlCl 36H 2o, is stirred to dissolving, then is incubated 12 hours at the temperature of 110 DEG C; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, after centrifugal treating, then under 90 DEG C of conditions, with Ethanol activation 24 hours, vacuum-drying, obtained metal amides organic backbone.Its X-ray diffractogram, infrared spectrogram, SEM, TEM figure and isothermal adsorption desorption curve figure are shown in accompanying drawing 1,2,3 and 4 respectively.
2, the preparation of modified bismaleimide resin cured article
0.087g metal amides organic backbone embodiment 1 step 1 prepared joins 37g2, and in 2 '-diallyl bisphenol, ultrasonic agitation dispersion 30min, obtains mixture A; By 50gN, N'-4,4 '-diphenyl methane dimaleimide adds mixture A, stirs, and at 140 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtains performed polymer; By performed polymer vacuum defoamation 10min at 140 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.Its specific inductivity-frequency curve, dielectric loss-frequency curve, shock strength, storage modulus-temperature variation curve and flexural strength are respectively see accompanying drawing 5,6,7,8 and 9.
Comparative example 1, the preparation of metallic organic framework: under nitrogen protection condition, is dissolved in the DMF of 31mL by 0.558g terephthalic acid; At temperature 110 DEG C and agitation condition, add 0.510gAlCl 36H 2o, stirs 4 hours, at temperature 110 DEG C, be incubated 12 hours; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, centrifugal; Again under 90 DEG C of conditions, with Ethanol activation 24 hours, vacuum-drying, obtained metallic organic framework.Its X-ray diffractogram, infrared spectrogram are shown in attached Fig. 1 and 2 respectively.
See accompanying drawing 1, it is X-ray (XRD) diffractogram of the metallic organic framework of comparative example 1 synthesis and the metal amides organic backbone of embodiment 1 synthesis.As seen from the figure, two kinds of metallic organic frameworks have identical diffraction pattern, illustrate that they have identical metallic organic framework elementary cell.
See accompanying drawing 2, it is the infrared spectrogram of the metallic organic framework of comparative example 1 synthesis and the metal amides organic backbone of embodiment 1 synthesis.1600cm -1and 1417cm -1the absorption peak at place is the asymmetric stretching vibration ν as (COO of hydroxy-acid group (-COOH) in terephthalic acid respectively _) and symmetrical stretching vibration ν s (COO _), 1581cm -1and 1400cm -1the absorption peak at place is respectively the asymmetric stretching vibration ν as (COO of-COOH in the amino terephthalic acid of 2- _) and symmetrical stretching vibration ν s (COO _).In general, the coordination mode of-COOH and metallic cation can divide three kinds, by its asymmetric stretching vibration ν as (COO _) and symmetrical stretching vibration ν s (COO _) the scope of difference (Δ) can draw.As Δ > 200cm -1monodentate ligand, Δ < 110cm -1be bidentate ligands, Δ is at 138 ~ 200cm -1in scope, then representative forms bridge joint chain.In metallic organic framework and metal amides organic backbone, the asymmetric stretching vibration ν as (COO of-COOH _) and symmetrical stretching vibration ν s (COO _) Δ value be respectively 183cm -1and 181cm -1, show carboxylic acid organic ligand and Al in metallo-organic framework 3+form bridge joint coordination.
See accompanying drawing 3, it is TEM and the SEM photo of the metal amides organic backbone that the present embodiment 1 synthesizes, and therefrom have crystal formation as seen, and the particle diameter of metal amides organic backbone is at about 100 ~ 200nm.
See accompanying drawing 4, it is the isothermal adsorption desorption curve figure of the metal amides organic backbone that the present embodiment 1 synthesizes.Its BET specific surface area is 171.78m 2/ g, much smaller than the value 1969m in document 2/ g, what therefore the present invention obtained is the metallic organic framework that duct is little, particle diameter is little.
Embodiment 2
The preparation of modified bismaleimide resin cured article
Metal amides organic backbone 0.261g embodiment 1 prepared joins 37g2, and in 2 '-diallyl bisphenol, ultrasonic agitation dispersion 30min, obtains mixture A; By 50gN, N'-4,4 '-diphenyl methane dimaleimide adds mixture A, stir, at 140 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 140 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.Its specific inductivity-frequency curve, dielectric loss-frequency curve, shock strength, storage modulus-temperature variation curve and flexural strength are respectively see accompanying drawing 5,6,7,8 and 9.
Comparative example 2, the preparation of bimaleimide resin: by 37g2,2 '-diallyl bisphenol and 50gN, N'-4,4 '-diphenyl methane dimaleimide, stir, at 140 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 140 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain bimaleimide resin.Its specific inductivity-frequency curve, dielectric loss-frequency curve, shock strength, storage modulus-temperature variation curve and flexural strength are respectively see accompanying drawing 5,6,7,8 and 9.
See accompanying drawing 5, it is the specific inductivity-frequency curve of the modified bismaleimide resin cured article that bimaleimide resin, embodiment 1 and 2 that comparative example 2 provides provide.Compared to the bimaleimide resin that comparative example 2 provides, the modified bismaleimide resin cured article that embodiment 1 and embodiment 2 provide has lower specific inductivity in whole range of frequency.Such as, during 100Hz, the specific inductivity of the bimaleimide resin that comparative example 2 provides is 3.78, and the specific inductivity of the modified bismaleimide resin cured article that embodiment 1 and embodiment 2 provide is respectively 3.17 and 3.15.
See accompanying drawing 6, it is the dielectric loss-frequency curve of the modified bismaleimide resin cured article that bimaleimide resin, embodiment 1 and 2 that comparative example 2 provides provide.During 100Hz, the dielectric loss of the bimaleimide resin that comparative example 2 provides is 0.0063, the dielectric loss of the modified bismaleimide resin that embodiment 1 and embodiment 2 provide only 0.0009 and 0.0004.
See accompanying drawing 7, it is the shock strength of the modified bismaleimide resin cured article that bimaleimide resin, embodiment 1 and 2 that comparative example 2 provides provide.As can be seen from the figure, the bimaleimide resin that the shock strength of the modified bismaleimide resin cured article that embodiment 1 and 2 provides provides higher than comparative example 2, this is because metal amides organic backbone is as organic inorganic hybridization rigid particles, can be effectively dispersed in resin matrix, and due to its particle diameter little, can effective toughening model+.
See accompanying drawing 8, it is that the storage modulus of the modified bismaleimide resin cured article that bimaleimide resin, embodiment 1 and 2 that comparative example 2 provides provide varies with temperature figure.Can find out, the storage modulus of the bimaleimide resin that the storage modulus of the modified bismaleimide resin cured article that embodiment 1 and embodiment 2 provide all provides higher than comparative example 2, this is because metal amides organic backbone belongs to rigid particles, the mechanical property of self is given prominence to, the rigidity of resin can be made to improve, illustrate that metal amides organic backbone is while toughening model+, improves the rigidity of resin.Known by reference to the accompanying drawings, modified resin prepared by the present invention is all improved in toughness and rigidity two.This conclusion can be confirmed further from flexural strength.
See accompanying drawing 9, it is the flexural strength figure of the modified bismaleimide resin cured article that bimaleimide resin, embodiment 1 and 2 that comparative example 2 provides provide.The bimaleimide resin that the flexural strength of the modified bismaleimide resin cured article that embodiment 1 and 2 provides provides higher than comparative example 2, illustrates that modified bimaleimide resin improves toughness and rigidity.
Embodiment 3
1, the preparation of metal amides organic backbone
Under nitrogen protection condition, amino for the 2-of 0.217g terephthalic acid is dissolved in the DMF of 31mL; At temperature 110 DEG C and agitation condition, add 0.724gAlCl 36H 2o, stirs 4 hours, at temperature 110 DEG C, be incubated 12 hours; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, centrifugal; Again under 90 DEG C of conditions, with Ethanol activation 22 hours, lyophilize, obtained metal amides organic backbone.
2, the preparation of modified bismaleimide resin cured article
0.080g metal amides organic backbone embodiment 3 step 1 prepared joins 2 of 30g, and in 2 '-diallyl bisphenol, ultrasonic agitation dispersion 30min, obtains mixture A; By 50gN, N'-4,4 '-diphenyl methane dimaleimide adds mixture A, stir, at 130 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 140 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.
Embodiment 4
1, the preparation of metal amides organic backbone
Under nitrogen protection condition, amino for 0.272g2-terephthalic acid is dissolved in the DMF of 31mL; At temperature 150 DEG C and agitation condition, add 0.724gAlCl 36H 2o, stirs 3 hours, at temperature 150 DEG C, be incubated 11.5 hours; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, centrifugal; Again under 88 DEG C of conditions, with Ethanol activation 24 hours, vacuum-drying, obtained metal amides organic backbone.
2, the preparation of modified bismaleimide resin cured article
0.261g metal amides organic backbone embodiment 4 step 1 prepared joins 2 of 37g, and in 2 '-diallyl bisphenol, ultrasonic agitation dispersion 30min, obtains mixture A; By 50gN, N'-4,4 '-diphenyl methane dimaleimide adds mixture A, stir, at 138 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 140 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.
Embodiment 5
1, the preparation of metal amides organic backbone
Under nitrogen protection condition, amino for the 2-of 0.380g terephthalic acid is dissolved in the DMF of 31mL; At temperature 110 DEG C and agitation condition, add 0.724gAlCl 36H 2o, stirs 4 hours, at temperature 110 DEG C, be incubated 11.5 hours; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, centrifugal; Again under 90 DEG C of conditions, with Ethanol activation 24 hours, vacuum-drying, obtained metal amides organic backbone.
2, the preparation of modified bismaleimide resin cured article
0.465g metal amides organic backbone embodiment 5 step 1 prepared joins 2 of 43g, and in 2 '-diallyl bisphenol, ultrasonic agitation dispersion 30min, obtains mixture A; By 50gN, N'-4,4 '-diphenyl methane dimaleimide adds mixture A, stir, at 130 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 140 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.
Embodiment 6
1, the preparation of metal amides organic backbone
Under nitrogen protection condition, amino for the 2-of 0.217g terephthalic acid is dissolved in the DMF of 40mL; At temperature 120 DEG C and agitation condition, add 0.724gAlCl 36H 2o, stirs 3 hours, at temperature 120 DEG C, be incubated 10 hours; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, centrifugal; Again under 85 DEG C of conditions, with Ethanol activation 22 hours, lyophilize, obtained metal amides organic backbone.
2, the preparation of modified bismaleimide resin cured article
0.560g metal amides organic backbone embodiment 6 step 1 prepared joins 2 of 30g, and in 2 '-diallyl bisphenol, ultrasonic agitation dispersion 30min, obtains mixture A; By 50gN, N'-4,4 '-diphenyl methane dimaleimide adds mixture A, stir, at 140 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 140 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.
Embodiment 7
1, the preparation of metal amides organic backbone
Under nitrogen protection condition, amino for the 2-of 0.272g terephthalic acid is dissolved in the DMF of 40mL; At temperature 120 DEG C and agitation condition, add 0.724gAlCl 36H 2o, stirs 4 hours, at temperature 120 DEG C, be incubated 12 hours; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, centrifugal; Again under 90 DEG C of conditions, with Ethanol activation 24 hours, lyophilize, obtained metal amides organic backbone.
2, the preparation of modified bismaleimide resin cured article
0.870g metal amides organic backbone embodiment 7 step 1 prepared joins 2 of 37g, and in 2 '-diallyl bisphenol, ultrasonic agitation dispersion 30min, obtains mixture A; By 50gN, N'-4,4 '-diphenyl methane dimaleimide adds mixture A, stir, at 140 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 140 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.
Embodiment 8
1, the preparation of metal amides organic backbone
Under nitrogen protection condition, amino for the 2-of 0.380g terephthalic acid is dissolved in the DMF of 40mL; At temperature 110 DEG C and agitation condition, add 0.724gAlCl 36H 2o, stirs 4 hours, at temperature 110 DEG C, be incubated 15 hours; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, centrifugal; Again under 90 DEG C of conditions, with Ethanol activation 24 hours, vacuum-drying, obtained metal amides organic backbone.
2, the preparation of modified bismaleimide resin cured article
0.651g metal amides organic backbone embodiment 8 step 1 prepared joins 2 of 43g, and in 2 '-diallyl bisphenol, ultrasonic agitation dispersion 30min, obtains mixture A; By 50gN, N'-4,4 '-diphenyl methane dimaleimide adds mixture A, stir, at 145 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 140 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.
Embodiment 9
1, the preparation of metal amides organic backbone
Under nitrogen protection condition, amino for the 2-of 0.217g terephthalic acid is dissolved in the DMF of 62mL; At temperature 130 DEG C and agitation condition, add 0.724gAlCl 36H 2o, stirs 2 hours, at temperature 130 DEG C, be incubated 12 hours; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, centrifugal; Again under 90 DEG C of conditions, with Ethanol activation 24 hours, vacuum-drying, obtained metal amides organic backbone.
2, the preparation of modified bismaleimide resin cured article
0.240g metal amides organic backbone embodiment 9 step 1 prepared joins 30g2, and in 2 '-diallyl bisphenol, ultrasonic agitation dispersion 30min, obtains mixture A; By 50gN, N'-4,4'-Diphenyl Ether Bismaleimide adds mixture A, stir, at 140 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 140 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.
Embodiment 10
1, the preparation of metal amides organic backbone
Under nitrogen protection condition, amino for the 2-of 0.380g terephthalic acid is dissolved in the DMF of 62mL; At temperature 150 DEG C and agitation condition, add 0.724gAlCl 36H 2o, stirs 4 hours, at temperature 150 DEG C, be incubated 10 hours; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, centrifugal; Again under 85 DEG C of conditions, with Ethanol activation 22 hours, vacuum-drying, obtained metal amides organic backbone.
2, the preparation of modified bismaleimide resin cured article
0.465g metal amides organic backbone embodiment 10 step 1 prepared joins 43g2, and in 2 '-diallyl bisphenol, ultrasonic agitation dispersion 30min, obtains mixture A; By 20gN, N'-4,4 '-diphenyl methane dimaleimide and 30gN, N'-4,4'-Diphenyl Ether Bismaleimide adds mixture A, stir, at 130 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 140 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.
Embodiment 11
1, the preparation of metal amides organic backbone
Under nitrogen protection condition, amino for the 2-of 0.326g terephthalic acid is dissolved in the DMF of 40mL; At temperature 120 DEG C and agitation condition, add 0.724gAlCl 36H 2o, stirs 4 hours, at temperature 120 DEG C, be incubated 15 hours; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, centrifugal; Again under 90 DEG C of conditions, with Ethanol activation 24 hours, lyophilize, obtained metal amides organic backbone.
2, the preparation of modified bismaleimide resin cured article
0.560g metal amides organic backbone embodiment 11 step 1 prepared joins 30g2, and in 2 '-diallyl bisphenol S, ultrasonic agitation dispersion 30min, obtains mixture A; By 50gN, N'-4,4'-Diphenyl Ether Bismaleimide adds mixture A, stir, at 138 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 145 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.
Embodiment 12
1, the preparation of metal amides organic backbone
Under nitrogen protection condition, amino for 0.326g2-terephthalic acid is dissolved in the DMF of 40mL; At temperature 110 DEG C and agitation condition, add 0.724gAlCl 36H 2o, stirs 3 hours, at temperature 110 DEG C, be incubated 12 hours; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, centrifugal; Again under 90 DEG C of conditions, with Ethanol activation 20 hours, vacuum-drying, obtained metal amides organic backbone.
2, the preparation of modified bismaleimide resin cured article
0.870g metal amides organic backbone embodiment 12 step 1 prepared joins 2 of 7g, 2 '-diallyl bisphenol S and 30g2, and in 2 '-diallyl bisphenol, ultrasonic agitation dispersion 30min, obtains mixture A; By 50gN, N'-4,4 '-diphenyl methane dimaleimide adds mixture A, stir, at 145 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 140 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.
Embodiment 13
1, the preparation of metal amides organic backbone
Under nitrogen protection condition, amino for the 2-of 0.326g terephthalic acid is dissolved in the DMF of 62mL; At temperature 120 DEG C and agitation condition, add 0.724gAlCl 36H 2o, stirs 4 hours, at temperature 120 DEG C, be incubated 12 hours; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, centrifugal; Again under 88 DEG C of conditions, with Ethanol activation 20 hours, vacuum-drying, obtained metal amides organic backbone.
2, the preparation of modified bismaleimide resin cured article
0.651g metal amides organic backbone embodiment 13 step 1 prepared joins 2 of 13g, 2 '-diallyl bisphenol S and 30g2, and in 2 '-diallyl bisphenol, ultrasonic agitation dispersion 30min, obtains mixture A; By 50gN, N'-4,4 '-diphenyl methane dimaleimide adds mixture A, stir, at 150 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 140 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.
Embodiment 14
1, the preparation of metal amides organic backbone
Under nitrogen protection condition, amino for the 2-of 0.204g terephthalic acid and 0.068g terephthalic acid are dissolved in the DMF of 40mL; At temperature 130 DEG C and agitation condition, add 0.724gAlCl 36H 2o, stirs 2 hours, at temperature 130 DEG C, be incubated 15 hours; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, centrifugal; Again under 90 DEG C of conditions, with Ethanol activation 24 hours, vacuum-drying, obtained metal amides organic backbone.
2, the preparation of modified bismaleimide resin cured article
0.400g metal amides organic backbone embodiment 14 step 1 prepared joins 2 of 10g, 2 '-diallyl bisphenol S and 20g2, and in 2 '-diallyl bisphenol, ultrasonic agitation dispersion 30min, obtains mixture A; By 50gN, N'-4,4 '-diphenyl methane dimaleimide adds mixture A, stir, at 150 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 140 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.
Embodiment 15
1, the preparation of metal amides organic backbone
Under nitrogen protection condition, 0.163g terephthalic acid and the amino terephthalic acid of 0.054g2-are dissolved in the DMF of 40mL; At temperature 130 DEG C and agitation condition, add 0.724gAlCl 36H 2o, stirs 4 hours, at temperature 130 DEG C, be incubated 10 hours; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, centrifugal; Again under 85 DEG C of conditions, with Ethanol activation 24 hours, lyophilize, obtained metal amides organic backbone.
2, the preparation of modified bismaleimide resin cured article
0.400g metal amides organic backbone embodiment 15 step 1 prepared joins 2 of 17g, 2 '-diallyl bisphenol S and 13g2, and in 2 '-diallyl bisphenol, ultrasonic agitation dispersion 30min, obtains mixture A; By 50gN, N'-4,4 '-diphenyl methane dimaleimide adds mixture A, stir, at 150 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 140 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.
Embodiment 16
1, the preparation of metal amides organic backbone
Under nitrogen protection condition, 0.180g terephthalic acid and the amino terephthalic acid of 0.200g2-are dissolved in the DMF of 40mL; At temperature 130 DEG C and agitation condition, add 0.724gAlCl 36H 2o, stirs 4 hours, at temperature 130 DEG C, be incubated 12 hours; After reaction terminates, naturally cool to room temperature, after filtration, adopt washing with alcohol, centrifugal; Again under 90 DEG C of conditions, with Ethanol activation 24 hours, vacuum-drying, obtained metal amides organic backbone.
2, the preparation of modified bismaleimide resin cured article
0.279g metal amides organic backbone embodiment 16 step 1 prepared joins 43g2, and in 2 '-diallyl bisphenol, ultrasonic agitation dispersion 30min, obtains mixture A; By 50gN, N'-4,4 '-diphenyl methane dimaleimide adds mixture A, stir, at 145 DEG C down to bismaleimides melting, after pre-polymerization 45min, obtain performed polymer, by performed polymer vacuum defoamation 10min at 142 DEG C, then performed polymer is poured in preheated mould, then at 140 DEG C vacuum defoamation 20min; According to 150 DEG C/2 hours+180 DEG C/2 hours+200 DEG C/2 hours+220 DEG C/2 hours and 240 DEG C/4 hours technique be cured respectively with aftertreatment after, namely obtain a kind of modified bismaleimide resin.

Claims (6)

1. a preparation method for modified bismaleimide resin, is characterized in that comprising following steps:
(1) under nitrogen protection condition, by mol, amino for 0.4 ~ 0.7 part of 2-terephthalic acid is dissolved in 0.4 ~ 0.8 part of DMF, is under the condition of 110 ~ 150 DEG C in temperature, adds 1 part of AlCl 36H 2o, is stirred to dissolving, then insulation reaction 10 ~ 15 hours, after naturally cooling to room temperature, carries out filtering, washs, centrifugal treating, then is, under the condition of 85 ~ 90 DEG C, use Ethanol activation process, obtain metal amides organic backbone after drying in temperature;
(2) the metal amides organic backbone that step (1) is obtained is mixed with diallyl phenyl compound, obtain mixture A;
(3) being joined by bismaleimides in mixture A, is mix under the condition of 130 ~ 150 DEG C in temperature, through solidification and aftertreatment, obtains a kind of modified bismaleimide resin.
2. the preparation method of a kind of modified bismaleimide resin according to claim 1, is characterized in that: described bismaleimides is N, N'-4,4 '-diphenyl methane dimaleimide, N, one in N'-4,4'-Diphenyl Ether Bismaleimide, or their arbitrary combination.
3. the preparation method of a kind of modified bismaleimide resin according to claim 1, it is characterized in that: described diallyl phenyl compound is 2,2 '-diallyl bisphenol, 2, the one in 2 '-diallyl bisphenol S, or their arbitrary combination.
4. the preparation method of a kind of modified bismaleimide resin according to claim 1, is characterized in that: in molar ratio, and diallyl phenyl compound and bismaleimides are 0.7 ~ 1.0:1.
5. the preparation method of a kind of modified bismaleimide resin according to claim 1, is characterized in that: in mass ratio, and the quality sum of diallyl phenyl compound and bismaleimides and metallic organic framework are 100:0.1 ~ 1.0.
6. by a kind of modified bismaleimide resin that claim 1 preparation method obtains.
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CN109563344A (en) * 2016-08-05 2019-04-02 日本化药株式会社 Maleimide resin composition, prepreg, its hardening thing and semiconductor device
CN111094228A (en) * 2017-08-22 2020-05-01 积水化学工业株式会社 Composition, process for producing molded article, and molded article
CN111094228B (en) * 2017-08-22 2024-02-09 积水化学工业株式会社 Composition, method for producing molded article, and molded article
CN110684353A (en) * 2019-09-24 2020-01-14 江苏立一新材料科技有限公司 High-performance friction material and application thereof
CN110684353B (en) * 2019-09-24 2021-12-03 江苏立一新材料科技有限公司 High-performance friction material and application thereof
CN112694750A (en) * 2020-12-28 2021-04-23 重庆工商大学 BT resin composite material containing nano MOFs and preparation method thereof
CN114018100A (en) * 2021-11-01 2022-02-08 安徽皓翔航空科技有限公司 Light aviation magazine and composite material for preparing same
CN118027135A (en) * 2024-04-11 2024-05-14 黑龙江八一农垦大学 Method for extracting selenium polypeptide from selenium-enriched rice

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