CN114149764A - Ultrathin high-toughness cyanate ester adhesive film and preparation method thereof - Google Patents
Ultrathin high-toughness cyanate ester adhesive film and preparation method thereof Download PDFInfo
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- CN114149764A CN114149764A CN202111525450.9A CN202111525450A CN114149764A CN 114149764 A CN114149764 A CN 114149764A CN 202111525450 A CN202111525450 A CN 202111525450A CN 114149764 A CN114149764 A CN 114149764A
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- cyanate ester
- cyanate
- adhesive film
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- 239000004643 cyanate ester Substances 0.000 title claims abstract description 75
- 239000002313 adhesive film Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 77
- 239000011347 resin Substances 0.000 claims abstract description 77
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 30
- 239000012745 toughening agent Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000004513 sizing Methods 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 238000005303 weighing Methods 0.000 claims abstract description 11
- 239000003292 glue Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 25
- 239000003822 epoxy resin Substances 0.000 claims description 24
- 229920000647 polyepoxide Polymers 0.000 claims description 24
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 229920000459 Nitrile rubber Polymers 0.000 claims description 13
- 229910021485 fumed silica Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- -1 polyethylene phthalate Polymers 0.000 claims description 10
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 7
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 7
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- 239000004697 Polyetherimide Substances 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004359 castor oil Substances 0.000 claims description 6
- 235000019438 castor oil Nutrition 0.000 claims description 6
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 229920001601 polyetherimide Polymers 0.000 claims description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 239000000440 bentonite Substances 0.000 claims description 5
- 229910000278 bentonite Inorganic materials 0.000 claims description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 4
- 239000004843 novolac epoxy resin Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- 229920006260 polyaryletherketone Polymers 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 description 7
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/35—Applications of adhesives in processes or use of adhesives in the form of films or foils for aeronautic or naval applications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides an ultrathin high-toughness cyanate ester adhesive film and a preparation method thereof, belonging to the technical field of composite materials and solving the technical problems that the high toughness of the cyanate ester adhesive film is ensured and the thickness of the adhesive film is greatly reduced or the adhesive film is attached to a carrier, wherein the ultrathin high-toughness cyanate ester adhesive film is prepared from 100 parts of cyanate ester resin, 5-50 parts of modified resin, 15-30 parts of toughening agent and 3-15 parts of thixotropic agent according to the mass part ratio; the preparation process comprises weighing raw materials; respectively adding different raw materials for polymerization; preparing a sizing material, and blade-coating the sizing material into a glue film with the thickness of 0.01-0.05 mm, wherein the ultrathin size of the glue film can keep good deformation, and the high-efficiency bonding effect is achieved, so that the production operation is facilitated, and the cost is saved.
Description
Technical Field
The invention belongs to the technical field of cyanate ester resin composite materials, and particularly relates to an ultrathin high-toughness cyanate ester adhesive film and a preparation method thereof.
Background
The Cyanate (CE) composite material has excellent comprehensive properties such as high heat resistance, low moisture absorption rate and space environment resistance, and has extremely low and stable dielectric constant epsilon (2.8-3.2) and dielectric loss tan delta (0.002-0.006) in a wide temperature (-160-220 ℃) and frequency range (104-1011 Hz), thereby becoming a preferred material for high-performance antenna covers and space structures. The radome is an important functional component of modern guided missiles, naval vessels and combat aircrafts, the honeycomb sandwich structure is an important structural form of the radome, the composite material skin and the honeycomb sandwich are bonded by mainly adopting a glue film, and the performance of the glue film directly influences the reliability, dielectric property and manufacturing process of the radome with the honeycomb sandwich structure.
At present, on the basis of a phenolic resin adhesive system and modified epoxy resin, adhesive film materials matched with Cyanate Ester (CE) type matrix resin performances (high temperature resistance, low dielectric constant and the like) are developed in China, and are applied to manufacturing of composite material skins of radomes, so that the requirements on bonding in the fields of aviation and aerospace are basically met.
However, with the rapid development of this field, aerospace has put more stringent requirements on structural materials. The challenge in the field is how to greatly reduce the thickness of the cyanate ester adhesive film while ensuring the high toughness of the cyanate ester adhesive film, and the cyanate ester adhesive film is not attached to a carrier.
Disclosure of Invention
In order to solve the problems in the prior art, a first object of the present invention is to provide an ultra-thin high-toughness cyanate ester adhesive film.
The technical scheme of the invention is as follows:
the ultrathin high-toughness cyanate ester adhesive film comprises, by mass, 100 parts of cyanate ester resin, 5-50 parts of modified resin, 15-30 parts of toughening agent and 3-15 parts of thixotropic agent.
The components of the invention preferably comprise 100 parts of cyanate ester resin, 10 parts of modified resin, 15 parts of toughening agent and 10 parts of thixotropic agent in parts by mass.
Preferably, the cyanate ester resin is one or more of bisphenol a cyanate ester, phenolic cyanate ester, bisphenol F cyanate ester, dicyclopentadiene cyanate ester, bisphenol M cyanate ester, or other multifunctional cyanate ester;
as a preferred aspect of the present invention, the modified resin is one or a combination of two or more of bisphenol a epoxy resin, novolac epoxy resin, p-aminophenol triglycidyl epoxy resin, amino tetrafunctional epoxy resin, silicone modified epoxy resin, polyurethane modified epoxy resin, or bismaleimide and a prepolymer thereof.
Preferably, the toughening agent is one or more of polyetherimide, polyphenyl ether, polysulfone, polyethylene phthalate, polyethylene terephthalate, polymethyl methacrylate, polyether sulfone, polyether ketone, polyarylether ketone and liquid nitrile rubber containing terminal groups.
Preferably, the thixotropic agent is one or more of fumed silica, castor oil, polyamide wax and organic bentonite.
The invention also aims to provide a preparation method of the ultrathin high-toughness cyanate ester adhesive film, which comprises the following steps:
step S1: weighing 100 parts of cyanate ester resin, 5-50 parts of modified resin, 15-30 parts of toughening agent and 3-15 parts of thixotropic agent according to the mass parts;
step S2: adding cyanate ester resin into a reaction device for heating, controlling the temperature to be 120-150 ℃, adding 5-50 parts of weighed modified resin into the cyanate ester resin after the temperature is stable, controlling the stirring speed to be 500-1000 r/min, and stirring for 30-90 min to obtain a mixed solution;
step S3: cooling the mixed solution obtained in the step S2 to 80-110 ℃, sequentially adding a toughening agent and a thixotropic agent into the mixed solution, fully stirring the mixed solution into a uniform system at the speed of 100-3000 r/min, and carrying out further polymerization reaction at the temperature of 80-110 ℃ to obtain a sizing material with viscosity;
step S4: and (4) blade-coating the glue stock obtained in the step (S3) at the temperature of 50-70 ℃ to form a film, and obtaining the final glue film.
In a preferred embodiment of the present invention, the thickness of the adhesive film obtained in step S4 is 0.01mm to 0.05 mm.
The invention has the following beneficial effects:
1. the ultrathin high-toughness cyanate ester adhesive film provided by the invention can greatly reduce the thickness of the adhesive film or solve the technical problem of attachment to a carrier while ensuring the high toughness of the cyanate ester adhesive film.
2. The toughening agent capable of reacting with main resin cyanate is added into the ultrathin high-toughness cyanate ester adhesive film, so that the toughness of the adhesive film is improved, and the normal-temperature shear strength can reach about 30 MPa.
3. The ultrathin high-toughness cyanate ester adhesive film provided by the invention improves the shape keeping capability of the adhesive film due to the addition of the thixotropic agent, and cannot be easily deformed due to pulling in the construction process.
4. The ultrathin high-toughness cyanate ester adhesive film provided by the invention has the thickness of 0.01-0.05 mm (the thickness of the existing adhesive film is more than 0.05mm), the ultrathin thickness can achieve the effect of efficient bonding, the phenomenon of glue overflow cannot occur in subsequent curing, in addition, the ultrathin thickness cannot influence the size of the whole product, and the production cost is reduced.
Detailed Description
While the preferred embodiments of the present invention will be described with reference to specific embodiments, the following examples are provided to aid the understanding of the methods of the present invention and are intended to cover modifications and improvements within the scope of the appended claims without departing from the spirit of the invention.
The ultrathin high-toughness cyanate ester adhesive film is prepared from 100 parts of cyanate ester resin, 5-50 parts of modified resin, 15-30 parts of toughening agent and 3-15 parts of thixotropic agent in parts by mass.
Wherein the cyanate resin is one or more of bisphenol A cyanate, phenolic cyanate, bisphenol F cyanate, dicyclopentadiene cyanate, bisphenol M cyanate or other multifunctional cyanate.
The modified resin is mainly (1) bisphenol A epoxy resin, linear phenolic epoxy resin, p-aminophenol triglycidyl epoxy resin, amino tetrafunctional epoxy resin, organosilicon modified epoxy resin and polyurethane modified epoxy resin. The system can form a certain amount of triazine ring structure for preserving the inherent performance advantages of the cyanate ester, and can also form a cross-linked network structure, so that the mechanical strength of the system is improved; meanwhile, a polyether structure with high flexibility is formed, so that the flexibility of the system is obviously improved; (2) bismaleimide and prepolymer thereof, wherein-OCN functional groups in cyanate react with active hydrogen on unsaturated double bonds in bismaleimide to obtain bismaleimide-triazine resin with an interpenetrating polymer network structure. The bismaleimide and the cyanate are copolymerized to generate a pyrimidine and pyridine structure, so that the impact resistance is favorably improved.
The toughening agent is one or more of Polyetherimide (PEI), polyphenylene oxide (PPO), Polysulfone (PS), polyethylene phthalate (PEP), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polyether sulfone (PES), polyether ketone (PEK), polyaryletherketone (PEK-C) and liquid nitrile rubber containing terminal groups. The addition of the toughening agent can reduce the brittleness of the cyanate ester resin and greatly improve the toughness of the adhesive.
The thixotropic agent is one or more of fumed silica, castor oil, polyamide wax and organic bentonite. The gas-phase silicon dioxide has a large amount of silicon hydroxyl, so that hydrogen bonds are formed between silicon dioxide to form a silicon dioxide network, and simultaneously, the silicon hydroxyl and the matrix can also form the hydrogen bonds, so that an interpenetrating network is formed, and good thickening performance is presented. The castor oil is dispersed and activated excessively, and long chains are intertwined with each other to form a thixotropic structure to play a thickening role. The polyamide wax mainly comprises a nonpolar aliphatic hydrocarbon part and a polar amide functional group, wherein an oxygen atom in the amide group has high electronegativity and is easy to form a hydrogen bond with a hydrogen atom in a hydrocarbon part, and the hydrogen bond can be formed among molecules so as to form thixotropy. The lamellar result of montmorillonite in the organic bentonite and the characteristic of swelling and dispersing the montmorillonite in an organic solvent into colloidal clay form gel, and the organic bentonite has good thickening property and thixotropy.
The preparation method of the ultrathin high-toughness cyanate ester adhesive film specifically comprises the following steps:
1. weighing 100 parts of cyanate ester resin, 5-50 parts of modified resin, 15-30 parts of toughening agent and 3-15 parts of thixotropic agent according to parts by mass;
2. adding cyanate ester resin into a reaction device for heating, controlling the temperature to be 120-150 ℃, adding 5-50 parts of weighed modified resin into the cyanate ester resin after the temperature is stable, controlling the stirring speed to be 500-1000 r/min, and stirring for 30-90 min to obtain a mixed solution;
3. cooling the mixed solution obtained in the previous step to 80-110 ℃, sequentially adding a toughening agent and a thixotropic agent into the mixed solution, fully stirring the mixed solution into a uniform system at the speed of 100-3000 r/min, and carrying out further polymerization reaction at the temperature of 80-110 ℃ to obtain a sizing material with viscosity;
4. and (3) blade-coating the sizing material obtained in the step at the temperature of 50-70 ℃ to form a film, thus obtaining the ultrathin high-toughness cyanate adhesive film.
The thickness of the ultrathin high-toughness cyanate adhesive film prepared in the method is 0.01-0.05 mm.
The present invention is further illustrated by the following examples.
Example 1
Weighing 100 parts of cyanate ester resin, 10 parts of modified resin, 15 parts of toughening agent and 10 parts of thixotropic agent according to the mass parts;
the cyanate resin is bisphenol A type cyanate resin, the modified resin is linear novolac epoxy resin, the toughening agent is liquid nitrile rubber containing terminal groups, and the thixotropic agent is fumed silica.
The preparation method of the ultrathin high-toughness cyanate adhesive film comprises the following steps:
adding the weighed bisphenol A type cyanate ester resin into a reaction device for heating, controlling the temperature to be 140 ℃, adding 10 parts of the weighed linear phenolic epoxy resin after the temperature is stable, controlling the stirring speed to be 500r/min, and keeping for 75 min;
cooling the mixed solution to 110 ℃, sequentially adding 15 parts of weighed liquid nitrile rubber containing end groups and 10 parts of fumed silica, fully stirring at the speed of 2000r/min to obtain a uniform system, and carrying out further polymerization reaction at the temperature of 110 ℃ to obtain a rubber material with certain viscosity;
finally, the obtained sizing material is blade-coated at the temperature of 70 ℃ to form a film, and the ultrathin high-toughness cyanate adhesive film is obtained. The average thickness of the tested adhesive film is 0.015mm, and the normal-temperature tensile shear strength is 31.2 MPa.
Example 2
Weighing 100 parts of cyanate ester resin, 40 parts of modified resin, 15 parts of toughening agent and 10 parts of thixotropic agent according to the mass parts;
the cyanate resin is bisphenol A type cyanate resin, the modified resin is linear novolac epoxy resin, the toughening agent is liquid nitrile rubber containing terminal groups, and the thixotropic agent is fumed silica.
The preparation method of the ultrathin high-toughness cyanate adhesive film comprises the following steps:
adding the weighed bisphenol A type cyanate ester resin into a reaction device for heating, controlling the temperature to be 130 ℃, adding 40 parts of the weighed linear phenolic epoxy resin after the temperature is stable, controlling the stirring speed to be 800r/min, and keeping for 60 min;
cooling the mixed solution to 110 ℃, sequentially adding 15 parts of weighed liquid nitrile rubber containing end groups and 10 parts of fumed silica, fully stirring at the speed of 2500r/min to obtain a uniform system, and carrying out further polymerization reaction at the temperature of 110 ℃ to obtain a rubber material with certain viscosity;
finally, the obtained sizing material is blade-coated at the temperature of 70 ℃ to form a film, and the ultrathin high-toughness cyanate adhesive film is obtained. The average thickness of the tested adhesive film is 0.017mm, and the normal-temperature tensile shear strength is 32.1 MPa.
Example 3
Weighing 100 parts of cyanate ester resin, 20 parts of modified resin, 25 parts of toughening agent and 15 parts of thixotropic agent according to the mass parts;
the cyanate resin is prepared from the following components in a mass ratio of 90: 10 bisphenol A cyanate ester resin and phenolic cyanate ester, wherein the modified resin is linear phenolic epoxy resin, the toughening agent is liquid nitrile rubber containing terminal groups, and the thixotropic agent is fumed silica.
The preparation method of the ultrathin high-toughness cyanate adhesive film comprises the following steps:
adding the bisphenol A type cyanate ester resin and the phenolic aldehyde cyanate ester which are weighed according to the proportion into a reaction device for heating, controlling the temperature to be 140 ℃, adding the weighed 20 parts of the linear phenolic aldehyde epoxy resin after the temperature is stable, controlling the stirring speed to be 700r/min, and keeping for 45 min;
cooling the mixed solution to 90 ℃, sequentially adding 25 parts of weighed liquid nitrile rubber containing end groups and 15 parts of fumed silica, fully stirring at the speed of 2500r/min to obtain a uniform system, and carrying out further polymerization reaction at the temperature of 90 ℃ to obtain a rubber material with certain viscosity;
finally, the obtained sizing material is blade-coated at the temperature of 70 ℃ to form a film, and the ultrathin high-toughness cyanate adhesive film is obtained. The average thickness of the tested adhesive film is 0.018mm, and the normal-temperature tensile shear strength is 29.7 MPa.
Example 4
Weighing 100 parts of cyanate ester resin, 20 parts of modified resin, 15 parts of toughening agent and 15 parts of thixotropic agent according to the mass parts;
the cyanate resin is prepared from the following components in percentage by mass of 80: 20 bisphenol A cyanate ester resin and phenolic cyanate ester, wherein the modified resin is linear phenolic epoxy resin, the toughening agent is liquid nitrile rubber containing terminal groups, and the thixotropic agent is fumed silica.
The preparation method of the ultrathin high-toughness cyanate adhesive film comprises the following steps:
adding the bisphenol A type cyanate ester resin and the phenolic aldehyde cyanate ester which are weighed according to the proportion into a reaction device for heating, controlling the temperature to be 135 ℃, adding 20 parts of the weighed linear phenolic aldehyde epoxy resin after the temperature is stable, controlling the stirring speed to be 800r/min, and keeping the stirring speed for 80 min;
cooling the mixed solution to 105 ℃, sequentially adding 15 parts of weighed liquid nitrile rubber containing end groups and 15 parts of fumed silica, fully stirring at the speed of 2500r/min to obtain a uniform system, and carrying out further polymerization reaction at the temperature of 105 ℃ to obtain a rubber material with certain viscosity;
finally, the obtained sizing material is blade-coated at the temperature of 60 ℃ to form a film, and the ultrathin high-toughness cyanate adhesive film is obtained. The average thickness of the tested adhesive film is 0.025mm, and the normal-temperature tensile shear strength is 29.3 MPa.
Example 5
Weighing 100 parts of cyanate ester resin, 15 parts of modified resin, 15 parts of toughening agent and 5 parts of thixotropic agent according to the mass parts;
the cyanate resin is prepared from the following components in a mass ratio of 90: 10 bisphenol A cyanate ester resin and phenolic cyanate ester, wherein the modified resin is polyurethane modified epoxy resin, the toughening agent is liquid nitrile rubber containing terminal groups, and the thixotropic agent is fumed silica.
The preparation method of the ultrathin high-toughness cyanate adhesive film comprises the following steps:
adding the bisphenol A type cyanate ester resin and the phenolic cyanate ester which are weighed according to the proportion into a reaction device for heating, controlling the temperature to be 130 ℃, after the temperature is stable, adding 15 parts of the polyurethane modified epoxy resin which is weighed, controlling the stirring speed to be 600r/min, and keeping for 80 min;
cooling the mixed solution to 100 ℃, sequentially adding 15 parts of weighed liquid nitrile rubber containing end groups and 5 parts of fumed silica, fully stirring at the speed of 1000r/min to obtain a uniform system, and carrying out further polymerization reaction at the temperature of 100 ℃ to obtain a rubber material with certain viscosity;
finally, the obtained sizing material is blade-coated at the temperature of 70 ℃ to form a film, and the ultrathin high-toughness cyanate adhesive film is obtained. The average thickness of the tested adhesive film is 0.034mm, and the normal-temperature tensile shear strength is 29.9 MPa.
Example 6
Weighing 100 parts of cyanate ester resin, 5 parts of modified resin, 20 parts of toughening agent and 5 parts of thixotropic agent according to the mass parts;
the cyanate resin is prepared from the following components in a mass ratio of 90: 10 bisphenol A cyanate ester resin and phenolic cyanate ester, the modified resin is bismaleimide, the flexibilizer is polyetherimide, and the thixotropic agent is castor oil.
The preparation method of the ultrathin high-toughness cyanate adhesive film comprises the following steps:
adding the bisphenol A type cyanate ester resin and the phenolic cyanate ester which are weighed according to the proportion into a reaction device for heating, controlling the temperature to be 150 ℃, adding the weighed 5 parts of bismaleimide after the temperature is stable, controlling the stirring speed to be 500r/min, and keeping for 40 min;
cooling the mixed solution to 110 ℃, sequentially adding 20 parts of weighed polyetherimide and 5 parts of castor oil, fully stirring at the speed of 800r/min to obtain a uniform system, and carrying out further polymerization reaction at the temperature of 110 ℃ to obtain a rubber material with certain viscosity;
finally, the obtained sizing material is blade-coated at the temperature of 70 ℃ to form a film, and the ultrathin high-toughness cyanate adhesive film is obtained. The average thickness of the tested adhesive film is 0.037mm, and the normal-temperature tensile shear strength is 28.8 MPa.
Example 7
Weighing 100 parts of cyanate ester resin, 10 parts of modified resin, 20 parts of toughening agent and 10 parts of thixotropic agent according to the mass parts;
the cyanate resin is dicyclopentadiene cyanate, the modified resin is organosilicon modified epoxy resin, the toughening agent is polyethylene glycol terephthalate, and the thixotropic agent is polyamide wax.
The preparation method of the ultrathin high-toughness cyanate adhesive film comprises the following steps:
adding the weighed dicyclopentadiene cyanate into a reaction device for heating, controlling the temperature to be 120 ℃, adding 10 parts of the weighed organic silicon modified epoxy resin after the temperature is stable, controlling the stirring speed to be 1000r/min, and keeping the stirring speed for 90 min;
cooling the mixed solution to 80 ℃, sequentially adding 20 parts of weighed polyethylene terephthalate and 10 parts of weighed polyamide wax, fully stirring at the speed of 500r/min to obtain a uniform system, and carrying out further polymerization reaction at the temperature of 80 ℃ to obtain a rubber material with certain viscosity;
finally, the obtained sizing material is blade-coated at the temperature of 50 ℃ to form a film, and the ultrathin high-toughness cyanate adhesive film is obtained. The average thickness of the tested adhesive film is 0.017mm, and the normal-temperature tensile shear strength is 28.5 MPa. The above examples show that the ultrathin cyanate adhesive film prepared by the invention has good mechanical properties, all of which are about 30MPa, and meets the adhesive property and use requirements of the ultrathin cyanate adhesive film. The upper and lower limits and interval values of the raw materials and the upper and lower limits and interval values of the process parameters can all realize the invention, and examples are not listed here.
Claims (8)
1. An ultrathin high-toughness cyanate ester adhesive film is characterized in that: the adhesive comprises the following components, by mass, 100 parts of cyanate ester resin, 5-50 parts of modified resin, 15-30 parts of toughening agent and 3-15 parts of thixotropic agent.
2. The ultrathin high-toughness cyanate ester adhesive film according to claim 1, wherein: the adhesive comprises the following components, by mass, 100 parts of cyanate ester resin, 10 parts of modified resin, 15 parts of toughening agent and 10 parts of thixotropic agent.
3. The ultrathin high-toughness cyanate ester adhesive film according to claim 1, wherein: the cyanate resin is one or a combination of more of bisphenol A cyanate, phenolic cyanate, bisphenol F cyanate, dicyclopentadiene cyanate, bisphenol M cyanate or other multifunctional cyanate.
4. The ultrathin high-toughness cyanate ester adhesive film according to claim 1, wherein: the modified resin is one or a combination of bisphenol A epoxy resin, phenol novolac epoxy resin, p-aminophenol triglycidyl epoxy resin, amino tetrafunctional epoxy resin, organic silicon modified epoxy resin, polyurethane modified epoxy resin or bismaleimide and a prepolymer thereof.
5. The ultrathin high-toughness cyanate ester adhesive film according to claim 1, wherein: the toughening agent is one or a combination of more of polyetherimide, polyphenyl ether, polysulfone, polyethylene phthalate, polyethylene glycol terephthalate, polymethyl methacrylate, polyether sulfone, polyether ketone, polyaryletherketone and liquid nitrile rubber containing terminal groups.
6. The ultrathin high-toughness cyanate ester adhesive film according to claim 1, wherein: the thixotropic agent is one or the combination of more of fumed silica, castor oil, polyamide wax and organic bentonite.
7. The preparation method of the ultrathin high-toughness cyanate ester adhesive film according to any one of claims 1 to 6, characterized by comprising the following steps:
step S1: weighing 100 parts of cyanate ester resin, 5-50 parts of modified resin, 15-30 parts of toughening agent and 3-15 parts of thixotropic agent according to the mass parts;
step S2: adding cyanate ester resin into a reaction device for heating, controlling the temperature to be 120-150 ℃, adding 5-50 parts of weighed modified resin into the cyanate ester resin after the temperature is stable, controlling the stirring speed to be 500-1000 r/min, and stirring for 30-90 min to obtain a mixed solution;
step S3: cooling the mixed solution obtained in the step S2 to 80-110 ℃, sequentially adding a toughening agent and a thixotropic agent into the mixed solution, fully stirring the mixed solution into a uniform system at the speed of 100-3000 r/min, and carrying out further polymerization reaction at the temperature of 80-110 ℃ to obtain a sizing material with viscosity;
step S4: and (4) blade-coating the glue stock obtained in the step (S3) at the temperature of 50-70 ℃ to form a film, and obtaining the final glue film.
8. The preparation method of the ultrathin high-toughness cyanate ester adhesive film according to claim 7, wherein the preparation method comprises the following steps: the thickness of the glue film obtained in the step S4 is 0.01 mm-0.05 mm.
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