CN104804185A - Cyanate ester prepolymer used for preparing glue film and preparation method of cyanate ester prepolymer - Google Patents
Cyanate ester prepolymer used for preparing glue film and preparation method of cyanate ester prepolymer Download PDFInfo
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- CN104804185A CN104804185A CN201510201306.8A CN201510201306A CN104804185A CN 104804185 A CN104804185 A CN 104804185A CN 201510201306 A CN201510201306 A CN 201510201306A CN 104804185 A CN104804185 A CN 104804185A
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Abstract
The invention discloses a cyanate ester prepolymer used for preparing a glue film and a preparation method of the cyanate ester prepolymer, and relates to the technical field of polymer materials, in particular to a prepolymer composition and a preparation method thereof and aims to solve the technical problems of the existing method that the reaction temperature is high, the yield is low, and implosion easily occurs. The cyanate ester prepolymer for preparing the glue film is made of thermoplastic polysulfone resin and bisphenol A type cyanate ester prepolymer. The method for preparing cyanate ester prepolymer includes the following steps: thermoplastic polysulfone resin is added into liquid cyanate ester until thermoplastic polysulfone resin is totally dissolved; a polymerization catalyst is added for reacting; after the reaction is carried out for 2 hours, polymerization product is taken every 10 minutes and placed on a piece of isolation paper for 5 minutes; the polymerization reaction is ended when the product becomes transparent and can be stripped off from the isolation paper, and the cyanate ester prepolymer used for preparing the glue film is obtained. The invention further provides a method for preparing the cyanate ester prepolymer composition, and solves the problems of the existing process that the reaction temperature is high, the process is difficult to control, the yield is low, and implosion easily occurs.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of performed polymer composition and method of making the same.
Background technology
Cyanate ester resin has a structural and functional class performance resins material while of being the exploitation eighties in 20th century, and achieve commercialization the nineties, after this its application obtains fast development.
Cyanate ester monomer molecular formula
Cyanate ester resin, compared with the performance resins of maturation, has the good process of epoxy resin, strengthens the high-temperature behavior that bismaleimide resin is similar, the heatproof combustion resistance of resol.
Table 1. cyanate ester resin and other high-performance thermosetting resin fundamental propertys compare
| Performance | Epoxy | Phenolic aldehyde | Strengthen span | Cyanate |
| Density g/cm 3 | 1.2～1.25 | 1.24～1.32 | 1.2～1.3 | 1.1～1.35 |
| Use temperature DEG C | 180 | 200～250 | 200 | 200 |
| Tensile modulus GPa | 3.1～3.8 | 3～5 | 3.4～4.1 | 3.1～3.4 |
| DIELECTRIC CONSTANT ε 1MHz | 3.8～4.5 | 4.3～5.4 | 3.4～3.7 | 2.7～3.2 |
| Solidification value DEG C | 180 | 150～190 | 220～300 | 180～250 |
| The initial weightless temperature DEG C of TGA | 260～340 | 300～360 | 360～400 | 400～420 |
Special needs to be pointed out is: the dielectric properties of cyanate ester resin are that other resins are incomparable.Cyanate ester resin is after solidification, and reaction generates the triazine ring reticulated structure of high degree of symmetry:
Cyanate cured article symmetrical structure
The structure of this high degree of symmetry makes whole molecule form a resonance system, under electromagnetic field effect, shows extremely low dielectric loss (tan δ is 0.001 ~ 0.008) and low and stable specific inductivity; And when frequency changes, this molecular structure is insensitive to dielectric relaxor etc., has the feature of frequency of utilization wide (8 ~ 100GHz); The dielectric properties (-160 DEG C ~ 200 DEG C) in the temperature range of broadness of cyanate ester resin, change very little simultaneously.
Except thermotolerance is high, dielectric properties excellent except, the triazine ring structure of the high degree of symmetry of cyanate molecular skeleton also determines its product and has the low and isotropic advantage of agent of low hygroscopicity, dimensional stability, thermal expansivity, is therefore widely used as electromagnetic wave transparent material, structured material, high temperature resistant adhesives.At aerospace field, cyanate ester resin is mainly used in resistance to rupture technique for aircraft composite, sandwich of layers, RTM technique, radome, nose cone and antenna, the low property detected matrix material, telstar and the application of other spaces; Microelectronic encapsulation, multilayer circuit board and multi-chip module is mainly used at electronic applications.
According to product form, cyanate product is mainly divided into five classes such as prepreg, RTM resin, pasty state glue, glued membrane, composite foam.Wherein glued membrane (comprising membranaceous tackiness agent and membranaceous foamed adhesive) is most important sqtructural adhesive in aerospace industry application, has the advantages that quality is light, wave transmission rate is high, broadband properties is good.In honeycomb sandwich construction, the splicing of honeycomb core, filling, edge sealing, reinforcement and the fixing main of various inserts use membranaceous foamed adhesive; The membranaceous tackiness agent of bonding main use of high-performance blister covering and honeybee cored structure.
Cyanate glued membrane is one resin based on cyanate performed polymer, add the components such as curing catalysts, stopper, filler, thixotropic agent, toughner, whipping agent, the semi-solid state prepared through multiple techniques such as mixing, press molds also has certain flexible membranaceous tackiness agent.In cyanate glued membrane component, the component thing of most critical is cyanate performed polymer, the structure of performed polymer, the Determines processing performance of derived product (comprising film-forming properties, wetting property, trickling, tack, adhibit quality, storage characteristics etc.) and mechanical property, resistance toheat, dielectric properties.
CN 101402729 B discloses a kind of cyanate resin composition and preparation method thereof.Tetramethyl-bisphenol-f type cyanate is polymerized by the method at 190 ~ 220 DEG C, obtains tetramethyl-bisphenol-f type cyanate performed polymer.Again the performed polymer obtained and liquid bisphenol E-type cyanate are mixed to get a kind of composition, this composition is liquid at normal temperatures, can be applied to winding or RTM moulding process.
CN 102199289 B discloses a kind of preparation method of tetramethyl bisphenol F type cyanate resin prepolymer.In nitrogen atmosphere, by solid-state tetramethyl bisphenol F cyanate resin heating for dissolving; Add polymerization promotor, react at 150 ~ 170 DEG C; Cool when refractive index is 1.5750 ~ 1.5650, obtain liquid reactant; Add butanone again, non-volatile content >=65.36% in the product obtained.
Cyanate performed polymer product involved by above patent is liquid state, and the performed polymer used in cyanate glued membrane should be solvent-free pliable and tough semi-solid state product, and the cyanate performed polymer therefore involved by above patent can not as the base resin preparing glued membrane.
Patent CN 101935514 B discloses a kind of foam structural adhesive and preparation method thereof; wherein relate to the preparation method of cyanate performed polymer: by bisphenol A cyanate ester resin or bisphenol A cyanate ester resin and polysulfone resin mixture under nitrogen protection; heat in 160 ~ 180 DEG C and stir and react; until with glass stick dip polymkeric substance that reaction generates immediately sagging pull into 15 ~ 20cm rectangular time stop heating; discharging immediately; then cool, obtain cyanate performed polymer.In the process adopting this explained hereafter, prepolymerization reaction process is wayward, and reaction end is not easily held, and satisfactory semi-solid state, pliable and tough performed polymer yield rate are not high.Reason is: to be cyanate group (-OCN) be heated and three processes being polymerized to ring under catalyst action for the polyreaction of cyanate ester monomer, pre-polymerization process control be actually in monomer cure process certain a bit on termination reaction, the intermediate product obtained thus is exactly the performed polymer that we wish to obtain.Calculate according to DSC, cyanate polymerization reaction heat △ H is about 400J/g, the so high result caused of thermal discharge is: at 160 ~ 180 DEG C of reaction intervals, the rapid heat release of curing reaction, raise internal temperature further, namely complete hardening phase at short notice, moment " implode " phenomenon even occurs, decompose and discharge a large amount of toxic gas, pliable and tough intermediate product cannot be obtained.
In sum, develop that reaction process is gentle steadily, reaction end holds manageable cyanate performed polymer preparation technology and has important practical significance.
Summary of the invention
The object of the invention is to solve that existing method temperature of reaction is high, the difficult control of process, low, the easy generation " implode " of yield rate technical problem, provide a kind of cyanate performed polymer for the preparation of glued membrane and preparation method thereof.
Cyanate performed polymer for the preparation of glued membrane is made up according to the mass ratio of 10 ~ 35:100 of thermoplasticity polysulfones resinoid and bisphenol A cyanate ester prepolymer.
The monomer of described bisphenol A cyanate ester prepolymer is white crystal, and fusing point is 80 DEG C, and molecular structure is:
Described thermoplasticity polysulfones resinoid is polysulfone resin, polyethersulfone resin or polyaryl ether sulphone resin,
Wherein polysulfone resin, its molecular formula is:
in formula: 2≤n≤20,
Polyethersulfone resin, its molecular formula is:
in formula: 2≤n≤20,
Polyaryl ether sulphone resin, its molecular formula is:
in formula: 2≤n≤20.
The preparation method of the above-mentioned cyanate performed polymer for the preparation of glued membrane is as follows:
One, bisphenol A cyanate ester prepolymer is heated to be melted into homogeneous liquid state completely, obtains liquid cyanate;
Two, temperature be 110 ~ 120 DEG C, under the condition that stirs, thermoplasticity polysulfones resinoid is added until thermoplasticity polysulfones resinoid dissolves completely in liquid cyanate, add polymerizing catalyst, the addition of polymerizing catalyst is 1 ~ 5 ‰ of liquid cyanate quality, at 120 ~ 130 DEG C, carry out polyreaction 2 ~ 6h;
Three, after the polyreaction of step 2 carries out 2h, get on 5-10 gram of polymerisate to interleaving paper every 10min and place 5min, transparent when observing product, and when can strip down from interleaving paper, for polyreaction terminal, cooling, discharging, obtain the cyanate performed polymer for the preparation of glued membrane.
In step one, bisphenol A cyanate ester prepolymer is heated to melt completely at 80 DEG C ~ 120 DEG C.
Polymerization catalyzed described in step 2 is the mixture of acetylacetone copper and 4-nonyl phenol, and wherein the mass ratio of acetylacetone copper and 4-nonyl phenol is (1 ~ 5): 100.
To be cyanate group (-OCN) be heated and three processes being polymerized to ring under catalyst action for the solidification of cyanate ester monomer, pre-polymerization process control be actually in monomer cure process certain a bit on termination reaction, the intermediate product obtained thus, namely prepolymer.Calculate according to DSC, the hot △ H of curing reaction of bisphenol A cyanate ester is about 400J/g, the so high result caused of thermal discharge is: once temperature reaches on kick off temperature, the rapid heat release of curing reaction, raise internal temperature further, namely complete hardening phase at short notice, moment " implode " phenomenon even occurs, pliable and tough cyanate performed polymer cannot be obtained.
But the temperature spot that in cyanate polymerization process, existence two is crucial: " pre-polymerization temperature flex point " and " implode temperature flex point ".During lower than " pre-polymerization temperature flex point ", sluggish or do not react; When temperature is elevated to " implode temperature flex point ", speed of response strengthens rapidly, and internal temperature sharply raises, and moment " implode " phenomenon occurs, and decomposes and discharges a large amount of toxic gas.Between these two temperature flex points, there is the process window that narrow, this process window is exactly that polymeric reaction temperature of the present invention is interval, namely between 120 ~ 130 DEG C, in this temperature range, polymeric reaction temperature is lower, reaction temperature and steadily, reaction process easily controls, reaction process is as shown in Figure 1.
Carry out between 120 ~ 130 DEG C in polymerization process, along with the prolongation of time, transformation efficiency improves gradually, and product appearance changes as Fig. 2.
As can be seen from upper figure, too low or cross under high conversion, polymerisate is mechanically resistant material.The only termination reaction when transformation efficiency reaches particular value, just can obtain having the performed polymer of applicable compacting film forming of snappiness, ductility.
The determination of the present invention to polymerization terminal is realized by following steps: after polyreaction carries out 2h, take a morsel polymerisate on interleaving paper every 10min, room temperature places 5min, transparent when observing product, feel is pliable and tough and when can strip down from interleaving paper easily, be judged as polyreaction terminal, cooling, discharging.
The present invention does not contain any solvent for the preparation of the cyanate performed polymer of glued membrane, and being a kind of semi-solid state product with snappiness, ductility, tack, is the desirable feedstock preparing cyanate glued membrane (comprising membranaceous tackiness agent and membranaceous foamed adhesive).Present invention also offers the preparation method of described cyanate performed polymer composition, solve that existing technological reaction temperature is high, the difficult control of process, low, the easy generation " implode " of yield rate a difficult problem.
Accompanying drawing explanation
Fig. 1 is 120 ~ 130 DEG C, polymeric reaction temperature interval of the present invention reaction process figure;
Fig. 2 is 120 ~ 130 DEG C, polymeric reaction temperature interval of the present invention product appearance variation diagram.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment is made up according to the mass ratio of 10 ~ 35:100 of thermoplasticity polysulfones resinoid and bisphenol A cyanate ester prepolymer for the preparation of the cyanate performed polymer of glued membrane.
Embodiment two: present embodiment and embodiment one unlike the monomer molecule structure of described bisphenol A cyanate ester prepolymer are:
the mass ratio of thermoplasticity polysulfones resinoid and bisphenol A cyanate ester prepolymer is 15 ~ 25:100.Other is identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two are polysulfone resin, polyethersulfone resin or polyaryl ether sulphone resin unlike described thermoplasticity polysulfones resinoid,
Wherein polysulfone resin, its molecular formula is:
in formula: 2≤n≤20,
Polyethersulfone resin, its molecular formula is:
in formula: 2≤n≤20,
Polyaryl ether sulphone resin, its molecular formula is:
in formula: 2≤n≤20.Other is identical with one of embodiment one or two.
Embodiment four: the preparation method of the cyanate performed polymer for the preparation of glued membrane described in embodiment one is as follows:
One, bisphenol A cyanate ester prepolymer is heated to be melted into homogeneous liquid state completely, obtains liquid cyanate;
Two, temperature be 110 ~ 120 DEG C, under the condition that stirs, thermoplasticity polysulfones resinoid is added until thermoplasticity polysulfones resinoid dissolves completely in liquid cyanate, add polymerizing catalyst, the addition of polymerizing catalyst is 1 ~ 5 ‰ of liquid cyanate quality, at 120 ~ 130 DEG C, carry out polyreaction 2 ~ 6h;
Three, after the polyreaction of step 2 carries out 2h, get on 5 ~ 10g polymerisate to interleaving paper every 10min and place 5min, transparent when observing product, and when can strip down from interleaving paper, for polyreaction terminal, cooling, discharging, obtain the cyanate performed polymer for the preparation of glued membrane.
Embodiment five: bisphenol A cyanate ester prepolymer is heated to melt completely at 80 DEG C ~ 120 DEG C unlike in step one by present embodiment and embodiment four.Other is identical with embodiment four.
Embodiment six: present embodiment and embodiment four or five are the mixture of acetylacetone copper and 4-nonyl phenol unlike polymerization catalyzed described in step 2, and wherein the mass ratio of acetylacetone copper and 4-nonyl phenol is (1 ~ 5): 100.Other is identical with embodiment four or five.
The preparation method of polymerizing catalyst: add 1Kg4-nonyl phenol in 2.5L stainless steel cauldron, be heated to 100 ~ 120 DEG C, under agitation add 30g acetylacetone copper, maintenance system temperature is between 100 ~ 120 DEG C, after 2h, acetylacetone copper is dissolved in 4-nonyl phenol completely, and now system is black-and-blue uniform solution.
Embodiment seven: one of present embodiment and embodiment four to six are 115 DEG C unlike in step 2 in temperature, under the condition that stirs, add thermoplasticity polysulfones resinoid until thermoplasticity polysulfones resinoid dissolves completely in liquid cyanate.Other is identical with one of embodiment four to six.
Embodiment eight: one of present embodiment and embodiment four to seven are 2 ~ 4 ‰ of liquid cyanate quality unlike the addition of polymerizing catalyst in step 2.Other is identical with one of embodiment four to seven.
Embodiment nine: one of present embodiment and embodiment four to eight are 3 ‰ of liquid cyanate quality unlike the addition of polymerizing catalyst in step 2.Other is identical with one of embodiment four to eight.
Embodiment ten: one of present embodiment and embodiment four to nine carry out polyreaction 2 ~ 6h unlike in step 2 at 125 DEG C.Other is identical with one of embodiment four to nine.
Adopt following experimental verification effect of the present invention:
Experiment one:
Preparation method for the preparation of the cyanate performed polymer of glued membrane:
One, add 10Kg bisphenol A cyanate ester monomer in 20L stainless steel cauldron, heating and temperature control is between 80 ~ 120 DEG C, and after 2h, cyanate ester monomer is molten into transparent liquid gradually, obtains liquid cyanate;
Two, temperature be 110 ~ 120 DEG C, under the condition that stirs, add in liquid cyanate and add 1.6Kg polysulfone resin (PSU) in batches, 1.5h after, polysulfone resin (PSU) is dissolved in cyanate completely, now system is mixture that is opaque, uniform tackiness, add 1.5g polymerizing catalyst (preparation method is as embodiment six), at 120 ~ 130 DEG C, carry out polyreaction;
Three, after the polyreaction of step 2 carries out 2h, get on 5g polymerisate to interleaving paper every 10min and place 5min, when polyreaction carries out 3.5h, Product samples appearance transparent of getting, feel is pliable and tough and can strip down from interleaving paper easily, judge now as polyreaction terminal, cooling, discharging, obtain the cyanate performed polymer for the preparation of glued membrane.
After product room temperature places 1 week, do not have cyanate " crystallization " phenomenon, feel is pliable and tough, ductility good.
Experiment two:
Preparation method for the preparation of the cyanate performed polymer of glued membrane:
One, add 10Kg bisphenol A cyanate ester monomer in 20L stainless steel cauldron, between 80 ~ 120 DEG C, be molten into transparent liquid gradually, obtain liquid cyanate;
Two, temperature be 110 ~ 120 DEG C, under the condition that stirs, 2.0Kg polyethersulfone resin (PES) is added in liquid cyanate, dissolve completely after 2.0h, add 2.0g polymerizing catalyst (preparation method is as embodiment six), at 120 ~ 130 DEG C, carry out polyreaction;
Three, after the polyreaction of step 2 carries out 3h, get on 6g polymerisate to interleaving paper every 10min and place 5min, when polyreaction carries out 3.0h, observe product transparent, and when can strip down from interleaving paper, for polyreaction terminal, cooling, discharging, obtain the cyanate performed polymer for the preparation of glued membrane.
Experiment three:
Preparation method for the preparation of the cyanate performed polymer of glued membrane:
One, add 10Kg bisphenol A cyanate ester monomer in 20L stainless steel cauldron, between 80 ~ 120 DEG C, be molten into transparent liquid gradually, obtain liquid cyanate;
Two, temperature be 110 ~ 120 DEG C, under the condition that stirs, 1.5Kg polyaryl ether sulphone resin (PPSU) is added in liquid cyanate, dissolve completely after 1.5h, add 1.2g polymerizing catalyst (preparation method is as embodiment six), at 120 ~ 130 DEG C, carry out polyreaction;
Three, after the polyreaction of step 2 carries out 3h, get on 10 polymerisates to interleaving paper every 10min and place 5min, when polyreaction carries out 4.5h, observe product transparent, and when can strip down from interleaving paper, for polyreaction terminal, cooling, discharging, obtain the cyanate performed polymer for the preparation of glued membrane.
Claims (10)
1., for the preparation of the cyanate performed polymer of glued membrane, it is characterized in that the cyanate performed polymer for the preparation of glued membrane is made up according to the mass ratio of 10 ~ 35:100 of thermoplasticity polysulfones resinoid and bisphenol A cyanate ester prepolymer.
2., according to claim 1 for the preparation of the cyanate performed polymer of glued membrane, it is characterized in that the monomer molecule structure of described bisphenol A cyanate ester prepolymer is:
3., according to claim 1 for the preparation of the cyanate performed polymer of glued membrane, it is characterized in that described thermoplasticity polysulfones resinoid is polysulfone resin, polyethersulfone resin or polyaryl ether sulphone resin,
Wherein polysulfone resin, its molecular formula is:
in formula: 2≤n≤20,
Polyethersulfone resin, its molecular formula is:
in formula: 2≤n≤20,
Polyaryl ether sulphone resin, its molecular formula is:
in formula: 2≤n≤20.
4. described in claim 1 for the preparation of the preparation method of the cyanate performed polymer of glued membrane, it is characterized in that the method is as follows:
One, bisphenol A cyanate ester prepolymer is heated to be melted into homogeneous liquid state completely, obtains liquid cyanate;
Two, temperature be 110 ~ 120 DEG C, under the condition that stirs, thermoplasticity polysulfones resinoid is added until thermoplasticity polysulfones resinoid dissolves completely in liquid cyanate, add polymerizing catalyst, the addition of polymerizing catalyst is 1 ~ 5 ‰ of liquid cyanate quality, at 120 ~ 130 DEG C, carry out polyreaction 2 ~ 6h;
Three, after the polyreaction of step 2 carries out 2h, on 10min takes a morsel polymerisate to interleaving paper, 5min is placed, transparent when observing product, and when can strip down from interleaving paper, for polyreaction terminal, cooling, discharging, obtain the cyanate performed polymer for the preparation of glued membrane.
5., according to claim 4 for the preparation of the preparation method of the cyanate performed polymer of glued membrane, it is characterized in that in step one, bisphenol A cyanate ester prepolymer being heated to melt completely at 80 DEG C ~ 120 DEG C.
6. according to claim 4 for the preparation of the preparation method of the cyanate performed polymer of glued membrane, it is characterized in that the polymerization catalyzed mixture for acetylacetone copper and 4-nonyl phenol described in step 2, wherein the mass ratio of acetylacetone copper and 4-nonyl phenol is (1 ~ 5): 100.
7. according to claim 4,5 or 6 for the preparation of the preparation method of the cyanate performed polymer of glued membrane, it is characterized in that being 115 DEG C in temperature, under the condition that stirs, in liquid cyanate, adding thermoplasticity polysulfones resinoid until thermoplasticity polysulfones resinoid dissolves completely in step 2.
8. according to claim 4,5 or 6 for the preparation of the preparation method of the cyanate performed polymer of glued membrane, it is characterized in that the addition of polymerizing catalyst in step 2 is 2 ~ 4 ‰ of liquid cyanate quality.
9. according to claim 4,5 or 6 for the preparation of the preparation method of the cyanate performed polymer of glued membrane, it is characterized in that the addition of polymerizing catalyst in step 2 is 3 ‰ of liquid cyanate quality.
10. according to claim 4,5 or 6 for the preparation of the preparation method of the cyanate performed polymer of glued membrane, it is characterized in that at 125 DEG C, carrying out polyreaction 2 ~ 6h in step 2.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111500250A (en) * | 2020-05-11 | 2020-08-07 | 四川川环科技股份有限公司 | Preparation method of heat-resistant adhesive |
| CN112048247A (en) * | 2020-09-14 | 2020-12-08 | 黑龙江省科学院石油化学研究院 | Bismaleimide/cyanate ester foamed adhesive film, and preparation method and application thereof |
| CN114806175A (en) * | 2022-04-22 | 2022-07-29 | 川化集团有限责任公司 | Bisphenol A type cyanate ester resin modified polysulfone composite material and preparation method thereof |
| CN115746781A (en) * | 2022-11-22 | 2023-03-07 | 黑龙江省科学院石油化学研究院 | Modified bismaleimide/cyanate adhesive film and preparation method thereof |
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| US20040213980A1 (en) * | 2001-01-08 | 2004-10-28 | Babayan Eduard P. | Woven fabric with a modified ester resin for use as a wet friction liner |
| WO2010082658A1 (en) * | 2009-01-19 | 2010-07-22 | 味の素株式会社 | Resin composition |
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| CN102876268A (en) * | 2012-10-12 | 2013-01-16 | 黑龙江省科学院石油化学研究院 | Phenolic aldehyde type cyanate ester adhesive |
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| US20040213980A1 (en) * | 2001-01-08 | 2004-10-28 | Babayan Eduard P. | Woven fabric with a modified ester resin for use as a wet friction liner |
| WO2010082658A1 (en) * | 2009-01-19 | 2010-07-22 | 味の素株式会社 | Resin composition |
| CN101935514A (en) * | 2010-09-30 | 2011-01-05 | 黑龙江省科学院石油化学研究院 | Novel foam structural adhesive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111500250A (en) * | 2020-05-11 | 2020-08-07 | 四川川环科技股份有限公司 | Preparation method of heat-resistant adhesive |
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| CN112048247A (en) * | 2020-09-14 | 2020-12-08 | 黑龙江省科学院石油化学研究院 | Bismaleimide/cyanate ester foamed adhesive film, and preparation method and application thereof |
| CN114806175A (en) * | 2022-04-22 | 2022-07-29 | 川化集团有限责任公司 | Bisphenol A type cyanate ester resin modified polysulfone composite material and preparation method thereof |
| CN115746781A (en) * | 2022-11-22 | 2023-03-07 | 黑龙江省科学院石油化学研究院 | Modified bismaleimide/cyanate adhesive film and preparation method thereof |
| CN115746781B (en) * | 2022-11-22 | 2024-04-16 | 黑龙江省科学院石油化学研究院 | Modified bismaleimide/cyanate adhesive film and preparation method thereof |
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| CN104804185B (en) | 2017-05-17 |
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