CN113930199B - Toughening phenolic adhesive and preparation method and application thereof - Google Patents
Toughening phenolic adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN113930199B CN113930199B CN202111341953.0A CN202111341953A CN113930199B CN 113930199 B CN113930199 B CN 113930199B CN 202111341953 A CN202111341953 A CN 202111341953A CN 113930199 B CN113930199 B CN 113930199B
- Authority
- CN
- China
- Prior art keywords
- phenolic adhesive
- resin film
- toughening
- adhesive
- phenolic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 117
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 117
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 60
- 239000011347 resin Substances 0.000 claims abstract description 60
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 55
- 239000004744 fabric Substances 0.000 claims abstract description 32
- 239000011521 glass Substances 0.000 claims abstract description 32
- 239000003607 modifier Substances 0.000 claims abstract description 29
- 239000002270 dispersing agent Substances 0.000 claims abstract description 27
- 230000007704 transition Effects 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 35
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 23
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 238000010008 shearing Methods 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 6
- 239000002313 adhesive film Substances 0.000 abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008602 contraction Effects 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 3
- 229910052709 silver Inorganic materials 0.000 abstract description 3
- 239000004332 silver Substances 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 229920001568 phenolic resin Polymers 0.000 description 14
- 239000005011 phenolic resin Substances 0.000 description 14
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 13
- 238000004090 dissolution Methods 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 10
- 239000000806 elastomer Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 238000002679 ablation Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- -1 phenolic aldehyde Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- 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
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
-
- 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
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- 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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/14—Glass
- C09J2400/143—Glass in the substrate
-
- 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
- C09J2461/00—Presence of condensation polymers of aldehydes or ketones
Abstract
The invention provides a toughening phenolic adhesive, a preparation method and application thereof. Specifically, the invention provides a toughening phenolic adhesive which is prepared from raw materials of phenolic adhesive, nitrile rubber, a modifier and a dispersing agent. The invention also provides a preparation method of the toughening phenolic adhesive. The invention further provides a toughening type resin film prepared from the toughening type phenolic adhesive and glass cloth and application of the toughening type resin film as a toughening type strain transition layer. The phenolic adhesive selected by the invention serves as a stress concentration center at the interface between metal and composite material, can induce a large amount of silver marks and shear bands, consumes and absorbs energy generated by the solidification of interface resin and fills expansion/contraction difference caused by the mismatching of linear expansion of the material, so that the problem of interface debonding is avoided, and the temperature resistance level is improved by the modifier; the brittleness of the adhesive film is generally avoided, and the shearing resistance of the adhesive is improved when the adhesive is used as a strain transition layer.
Description
Technical Field
The invention belongs to the technical field of composite materials, relates to a toughening phenolic adhesive, a preparation method and application thereof, and particularly relates to an application of preparing a toughening phenolic adhesive and glass cloth into a toughening resin film and using the toughening resin film as a toughening strain transition layer.
Background
With the development of aerospace technology, space has become a "high point" for maintaining national security and benefits, and various countries are directing more and more eyes to the development of aircraft. The problem of heat protection is one of the most critical factors for determining the safety and smooth completion of various tasks of an aircraft, and ablation heat protection is popular all the time with the characteristics of simplicity and reliability, so that the ablation heat protection is always the focus of attention of aerospace institutions and experts in various countries.
The ablation material is a special material used on the outer surface of the reentry cabin of the aircraft and the inner surface of the engine, and is decomposed, melted, evaporated, sublimated and other physical and chemical changes under the action of heat flow, so that a large amount of heat is taken away by the pyrolysis loss of the material surface and the radiation of the carbonization layer, and the heat flow is prevented from being transmitted into the interior of the aircraft. Because of the short working time of the engine of the medium-short-range aircraft, various performances of the phenolic resin can meet performance requirements and the cost is low, the phenolic resin is still the preferred resin matrix of the heat protection material of the engine in the future.
Phenolic resins (collectively called phenols and aldehyde polycondensation products) are typical representatives of ablative materials and have been used hitherto as main matrix resins for resin-based ablative-resistant materials, because of their excellent mechanical properties, heat resistance, cold resistance, dimensional stability, molding processability, flame retardancy, low smoke and low production cost. However, due to the nature of crosslinking and curing of molecular chains, the problems of inherent brittleness and high polycondensation and curing shrinkage rate are caused, so that the problems of debonding with a metal interface and the like are often caused by mismatching of linear expansion coefficients when the composite material is integrally formed on a cabin body.
In engineering, in order to solve the problem of debonding, a 9621 rubber sheet or other epoxy or phenolic adhesives are often used as a strain isolation layer to solve the problem, but because the introduced new material can cause an increase in bonding interface (or brittleness of resin adhesive), and the specific modeling of the aircraft (cabin), a local stress concentration area is inevitably caused, so that the local debonding phenomenon still occurs.
Disclosure of Invention
In order to solve the above problems in the prior art, the first aspect of the present invention provides a toughening phenolic adhesive, which is prepared from phenolic adhesive, nitrile rubber, a modifier and a dispersant as raw materials.
The invention provides a preparation method of the toughening phenolic adhesive in the first aspect, which comprises the following steps:
(1) Adding ethanol which is 1.5 to 2.5 times of the mass of the phenolic adhesive, for example, 2 times of the mass of the phenolic adhesive and is used as a solvent into a first container, adding a dispersing agent into the solvent, dispersing and dissolving by ultrasonic wave, and then adding the phenolic adhesive into the first container for dissolving to obtain a phenolic adhesive solution;
(2) Putting nitrile rubber and a modifier into a second container and uniformly mixing to obtain solid powder;
(3) And (3) adding the solid powder prepared in the step (2) into the phenolic adhesive solution prepared in the step (1), and uniformly stirring to prepare the toughening phenolic adhesive.
The present invention provides, in a third aspect, a toughened resin film, characterized in that the resin film is produced by: the invention provides the toughening phenolic adhesive in the first aspect by taking glass cloth as a carrier and loading the glass cloth on the carrier.
The present invention provides in a fourth aspect a method for preparing the toughened resin film of the third aspect of the present invention, wherein the toughened phenolic adhesive of the first aspect of the present invention or the toughened phenolic adhesive prepared by the method of the second aspect of the present invention is supported on glass cloth as a carrier by a hot melt method to obtain the toughened resin film.
The invention provides in a fifth aspect the use of the toughened resin film of the third aspect of the invention or the toughened resin film prepared by the method of the fourth aspect of the invention as a toughened strain transition layer.
Compared with the prior art, the invention has at least the following advantages:
(1) The invention adopts the nitrile rubber, especially the nanometer nitrile rubber particles, and the average particle diameter is 50 to 100nm, the specific surface area is large, the surface energy is high, the interface area between the elastomer and the resin matrix is increased, and the compatibility of the elastomer and the resin matrix is improved.
(2) The nitrile rubber, especially carboxyl-terminated nitrile rubber filler, selected by the invention has the same functional group as the solvent, and can be better dispersed in the solvent. On the other hand, the phenolic adhesive can react with the polar functional groups of the phenolic adhesive to form strong intermolecular force, so that the dissolution of the phenolic adhesive is promoted.
(3) The nitrile rubber, especially carboxyl-terminated nitrile rubber filler, is added as a toughening elastomer, serves as a stress concentration center at the interface between metal and composite material, can induce a large amount of silver grains and shear bands, consumes and absorbs energy generated by curing interface resin (reduces the generation of internal stress) and fills the expansion/contraction difference caused by the linear expansion mismatch of the materials, thereby avoiding the problem of interface debonding.
(4) The modifier resorcinol adopted in the invention is crosslinked with a phenolic adhesive and carboxyl-terminated nitrile rubber when being cured after being added, so that the temperature resistance grade of the adhesive film prepared by the modifier resorcinol is improved.
(5) The large-grid glass cloth is introduced as a glue film carrier, so that brittleness of a glue film, namely a toughened resin film, is avoided. When the toughened resin film is used as a strain transition layer, the shearing resistance of the adhesive can be obviously improved.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As described above, the present invention provides in a first aspect a toughened phenolic adhesive prepared from phenolic adhesive, nitrile rubber, a modifier and a dispersant as raw materials.
The phenolic adhesive used in the present invention is commercially available, for example, from the Heilongjiang petrochemical institute, and has an average molecular weight of about 400 and a room temperature tensile shear strength of 11.6MPa.
In some preferred embodiments, the mass ratio of the raw materials is as follows: 100 parts of phenolic adhesive, 10 to 30 parts (e.g. 20 parts) of nitrile rubber, 10 to 30 parts (e.g. 20 parts) of modifier, 0.2 to 0.8 part (e.g. 0.3, 0.4, 0.5, 0.6 or 0.7 part) of dispersant.
In some more specific embodiments, the mass ratio of the raw materials is as follows: 100 parts of phenolic adhesive, 10 to 30 parts of carboxyl terminated nitrile rubber, 10 to 30 parts of modifier resorcinol and 0.5 part of dispersing agent.
In other preferred embodiments, the phenolic adhesive has an average molecular weight of 300 to 500 (e.g., 350, 400, or 450).
In other preferred embodiments, the phenolic adhesive has a room temperature tensile shear strength of 10MPa to 15MPa (e.g., 11, 12, 13, or 14 MPa). . In some preferred embodiments, the phenolic adhesive has an average molecular weight of 400 and a room temperature tensile shear strength of 11.6MPa.
In other preferred embodiments, the nitrile rubber is a carboxyl terminated nitrile rubber. The nitrile rubber can be a commercially available product, for example, nitrile rubber produced by Beijing chemical institute of petrochemical industry, china, and has an average particle diameter in the range of 50 to 100nm.
The inventor discovers that the invention adopts the nitrile rubber, especially the nanometer nitrile rubber particles, and the average particle diameter is 50 to 100nm, the specific surface area is large, the surface energy is high, the interface area between the elastomer and the phenolic adhesive is increased, and the compatibility of the elastomer and the phenolic adhesive is improved. Furthermore, the nitrile rubber, in particular the carboxyl terminated nitrile rubber filler, selected according to the invention has the same functional groups as the solvent and is better dispersible in the solvent. On the other hand, the nitrile rubber can react with the polar functional groups of the phenolic adhesive to form strong intermolecular force, so that the dissolution of the phenolic resin is promoted. In addition, the nitrile rubber, especially carboxyl-terminated nitrile rubber filler, selected by the invention is used as a toughening elastomer, and after the nitrile rubber filler is added, the nitrile rubber filler acts as a stress concentration center at the interface between metal and composite materials, can induce a large amount of silver grains and shear bands, consumes and absorbs energy generated by curing interface resin (reduces the generation of internal stress) and fills expansion/contraction difference caused by mismatching of linear expansion of materials, thereby avoiding the problem of interface debonding.
Thus, in some more preferred embodiments, the nitrile rubber has an average particle size of 50nm to 100nm (e.g., 60, 70, 80, or 90 nm). If the particle size is too large, the specific surface area is reduced, and the surface energy is low, resulting in a smaller interfacial area between the elastomer and the phenolic adhesive, thereby reducing the compatibility of the two. Since nitrile rubber acts as an elastomer as a stress concentration center, if the particle size is too small, the ability to consume and absorb interfacial energy is reduced.
In other preferred embodiments, the modifier is selected from one or more of resorcinol, boric acid, and silicone. The modifier can be crosslinked with phenolic resin and nitrile rubber such as carboxyl-terminated nitrile rubber in the material heating and curing process, so that the temperature resistance level of the adhesive film is improved. In some embodiments, resorcinol is selected as a modifier that, upon addition, cross-links with the phenolic resin and the nitrile rubber when cured, improving the temperature resistance rating of the adhesive film made therewith.
In still other alternative or further preferred embodiments, the dispersant is selected from one or more of polyvinyl alcohol, polyethylene glycol, methylpentanol (e.g. neopentyl alcohol).
The invention provides a preparation method of the toughening phenolic adhesive in the first aspect, which comprises the following steps:
(1) Adding ethanol which is 1.5 to 2.5 times of the mass of the phenolic adhesive, for example, 2 times of the mass of the phenolic adhesive and is used as a solvent into a first container, adding a dispersing agent into the solvent, dispersing and dissolving by ultrasonic wave, and then adding the phenolic adhesive into the first container for dissolving to obtain a phenolic adhesive solution;
(2) Putting nitrile rubber and a modifier into a second container and uniformly mixing to obtain solid powder;
(3) And (3) adding the solid powder prepared in the step (2) into the phenolic adhesive solution prepared in the step (1), and uniformly stirring to prepare the toughening phenolic adhesive.
The present invention provides, in a third aspect, a toughened resin film, characterized in that the resin film is produced by: the invention provides the toughening phenolic adhesive in the first aspect by taking glass cloth as a carrier and loading the glass cloth on the carrier.
The invention introduces glass cloth, especially large grid glass cloth, as a glue film carrier, thereby avoiding brittleness of the glue film, namely the toughened resin film. According to the invention, a filler such as nitrile rubber, especially carboxyl-terminated nitrile rubber, is added into a resin adhesive to prepare the toughened strain transition layer. When the toughened resin film is used as a strain transition layer, the shearing resistance of the adhesive can be obviously improved, and the problem of interfacial debonding after the composite material and the metal cabin are integrally formed can be solved.
In some preferred embodiments, the glass cloth is a large mesh glass cloth. Preferably, the glass cloth has an areal density of 60 to 100g/m 2 (e.g. 70, 80 or 90g/m 2 ) Preferably 80g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or the glass cloth has a thickness of 0.05 to 0.15mm (e.g., 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, or 0.14 mm), preferably 0.1mm.
The present invention provides in a fourth aspect a method for preparing the toughened resin film of the third aspect of the present invention, wherein the toughened phenolic adhesive of the first aspect of the present invention or the toughened phenolic adhesive prepared by the method of the second aspect of the present invention is supported on glass cloth as a carrier by a hot melt method to obtain the toughened resin film.
In some more specific embodiments, the method of preparing the toughened resin film comprises the steps of:
(1) Taking 2 times of ethanol serving as a solvent of a phenolic adhesive in a first container, adding 0.5 part of dispersing agent into the solvent, dispersing and dissolving by using ultrasonic waves, and taking 100 parts of phenolic adhesive in the first container for dissolving to prepare a phenolic adhesive solution;
(2) Taking a second container, putting 10 to 30 parts of carboxyl-terminated nitrile rubber and 10 to 30 parts of resorcinol serving as a modifier into the second container, and stirring and premixing for 0.5h by using a stirring paddle to ensure uniform stirring, so that the subsequent dissolution and mixing are facilitated, and solid powder is obtained;
(3) Dividing the mixed solid powder in the step (2) into 4 parts, sequentially adding the 4 parts into the solution prepared in the step (1), stirring and dispersing the solution for 15 minutes by ultrasonic waves once for each time until all parts of solid powder are added at last, and uniformly stirring the resin composition to obtain the toughening phenolic adhesive;
(4) And preparing the obtained toughening phenolic adhesive and large-grid glass cloth into a resin film with a carrier by using a hot melting method, wherein the obtained product is the toughening type resin film which can be used as a toughening type strain transition layer.
The invention provides in a fifth aspect the use of the toughened resin film of the third aspect of the invention or the toughened resin film prepared by the method of the fourth aspect of the invention as a toughened strain transition layer.
Examples
The invention is further illustrated below with reference to examples. In the following examples or comparative examples, polyvinyl alcohol (CAS 9002-89-5, available from Shanghai microphone Biochemical technology Co., ltd.) was used as a dispersant, a phenolic adhesive (average molecular weight of about 400, room temperature tensile shear strength of 11.6 MPa) available from Heilongjiang petrochemical institute was used, and a carboxyl terminated nitrile rubber powder (average particle diameter of 50 to 100 nm) available from Beijing chemical institute of petrochemical, china was used. However, it should be understood that these examples are for illustrative purposes only and the scope of the present invention is not limited to these examples.
Comparative example 1
(1) Phenolic adhesive (obtained from Heilongjiang petrochemical institute, average molecular weight of 400, room temperature tensile shear strength of 11.6MPa, unless otherwise specified, used in the examples and comparative examples) was mixed with large mesh glass cloth (surface density of 80g/m 2 The thickness of the resin film is 0.10mm, and the large-grid glass cloth is adopted in the examples and the comparative examples) to prepare a resin film with a carrier, namely a toughening phenolic resin film which can be used as a toughening strain transition layer;
(2) In order to represent the bonding capability between the strain transition layer and the metal cabin, the tensile and shearing strength data of the material are used for measuring indexes. The tensile shear test pieces were prepared from the material, and the tensile shear strength at room temperature and the tensile shear strength at 100℃were measured, and the results are shown in Table 1 below.
Example 1
(1) 1kg of absolute ethyl alcohol as a solvent was weighed into a first container, 2.5g of a dispersing agent (polyvinyl alcohol (CAS 9002-89-5, available from Shanghai Milin Biochemical technology Co., ltd., unless otherwise specified, the dispersing agent was used in the following examples) was added to the solvent and dissolved by ultrasonic dispersion, 500g of a phenolic adhesive (available from Heilongjiang petrochemical institute, average molecular weight of about 400, tensile shear strength at room temperature of 11.6 MPa) was weighed into the first container, and mixed to obtain a phenolic adhesive solution.
(2) 50g of carboxyl-terminated nitrile rubber powder (produced by Beijing chemical institute of petrochemical industry, china, average grain size of 50-100 nm) and 50g of modifier resorcinol are weighed into a second container, and are premixed for 0.5h by stirring paddles, so that uniform stirring is ensured, and subsequent dissolution and mixing are facilitated, and solid powder is obtained.
(3) And (3) dividing the mixed solid powder into 4 parts, sequentially adding the 4 parts into the phenolic adhesive solution prepared in the step (1), stirring and dispersing the mixture for 15 minutes by ultrasonic waves once every one part is added until all parts of powder are added at last, and uniformly stirring the resin composition to obtain the toughening phenolic adhesive.
(4) The obtained toughened phenolic adhesive and large-mesh glass cloth (surface density)The degree of the reaction is 80g/m 2 A thickness of 0.10 mm) to prepare a resin film with a carrier, and the obtained product is the toughened phenolic resin film which can be used as a toughened strain transition layer;
(5) In order to represent the bonding capability between the strain transition layer and the metal cabin, the tensile and shearing strength data of the material are used for measuring indexes. The tensile shear test pieces were prepared from the material, and the tensile shear strength at room temperature and the tensile shear strength at 100℃were measured, and the results are shown in Table 1 below.
Example 2
(1) 1kg of absolute ethyl alcohol serving as a solvent is weighed into a first container, 2.5g of dispersing agent is added into the solvent, and is dispersed and dissolved by ultrasonic wave, 500g of phenolic adhesive is weighed and dissolved into the first container, and the phenolic adhesive solution is obtained by mixing;
(2) 50g of carboxyl-terminated nitrile rubber powder and 150g of resorcinol modifier are weighed in a second container, and are premixed for 0.5h by stirring paddles, so that uniform stirring is ensured, and subsequent dissolution and mixing are facilitated, and solid powder is obtained.
(3) Dividing the mixed solid powder into 4 parts, sequentially adding the 4 parts into the phenolic adhesive solution prepared in the step (1), stirring and dispersing the mixture for 15 minutes by ultrasonic waves once every time until all parts of powder are added at last, and uniformly stirring the resin composition to obtain the toughening phenolic adhesive;
(4) Preparing the obtained toughening phenolic adhesive and large-grid glass cloth into a resin film with a carrier by using a hot melting method, wherein the obtained product is the toughening phenolic resin film which can be used as a toughening strain transition layer;
(5) The tensile shear test pieces were prepared from the material, and the tensile shear strength at room temperature and the tensile shear strength at 100℃were measured, and the results are shown in Table 1 below.
Example 3
(1) 1kg of absolute ethyl alcohol serving as a solvent is weighed into a first container, 2.5g of dispersing agent is added into the solvent, and is dispersed and dissolved by ultrasonic wave, 500g of phenolic adhesive is weighed and dissolved into the first container, and the phenolic adhesive solution is obtained by mixing;
(2) 150g of carboxyl-terminated nitrile rubber powder and 50g of resorcinol modifier are weighed in a second container, and are premixed for 0.5h by stirring paddles, so that uniform stirring is ensured, and subsequent dissolution and mixing are facilitated, and solid powder is obtained.
(3) Dividing the mixed solid powder in the step (2) into 4 parts, sequentially adding the 4 parts into the phenolic adhesive solution prepared in the step (1), stirring once every time, and dispersing by ultrasonic waves for 15 minutes until all parts of solid powder are added at last, and uniformly stirring the resin composition to obtain the toughening phenolic adhesive;
(4) And preparing the obtained toughening phenolic adhesive and large-grid glass cloth into a resin film with a carrier by using a hot melting method, wherein the obtained product is the toughening phenolic resin film which can be used as a toughening strain transition layer.
(5) The tensile shear test pieces were prepared from the material, and the tensile shear strength at room temperature and the tensile shear strength at 100℃were measured, and the results are shown in Table 1 below.
Example 4:
(1) 1kg of absolute ethyl alcohol serving as a solvent is weighed into a first container, 2.5g of dispersing agent is added into the solvent, and is dispersed and dissolved by ultrasonic wave, 500g of phenolic adhesive is weighed and dissolved into the first container, and the phenolic adhesive solution is obtained by mixing;
(2) 150g of carboxyl-terminated nitrile rubber powder and 150g of modifier resorcinol are weighed in a second container, and are premixed for 0.5h by stirring paddles, so that uniform stirring is ensured, and final dissolution and mixing are facilitated, and solid powder is obtained.
(3) Dividing the mixed solid powder in the step (2) into 4 parts, sequentially adding the 4 parts into the phenolic adhesive solution prepared in the step (1), stirring once every time, and dispersing by ultrasonic waves for 15 minutes until all parts of solid powder are added at last, and uniformly stirring the resin composition to obtain the toughening phenolic adhesive;
(4) Preparing the obtained toughening phenolic adhesive and large-grid glass cloth into a resin film with a carrier by using a hot melting method, wherein the obtained product is the toughening phenolic resin film which can be used as a toughening strain transition layer;
(5) The tensile shear test pieces were prepared from the material, and the tensile shear strength at room temperature and the tensile shear strength at 100℃were measured, and the results are shown in Table 1 below.
Example 5
(1) 1kg of absolute ethyl alcohol as a solvent was weighed into a first container, 2.5g of a dispersing agent (polyvinyl alcohol (CAS 9002-89-5, available from Shanghai Milin Biochemical technology Co., ltd., unless otherwise specified, the dispersing agent was used in the following examples) was added to the solvent and dissolved by ultrasonic dispersion, 500g of a phenolic adhesive (available from Heilongjiang petrochemical institute, average molecular weight of about 400, tensile shear strength at room temperature of 11.6 MPa) was weighed into the first container, and mixed to obtain a phenolic adhesive solution.
(2) 175g of carboxyl-terminated nitrile rubber powder (produced by Beijing chemical institute of petrochemical industry, china, average grain size of 50-100 nm) and 150g of modifier resorcinol are weighed into a second container, and are premixed for 0.5h by stirring paddles, so that uniform stirring is ensured, and subsequent dissolution and mixing are facilitated, and solid powder is obtained.
(3) And (3) dividing the mixed solid powder into 4 parts, sequentially adding the 4 parts into the phenolic adhesive solution prepared in the step (1), stirring and dispersing the mixture for 15 minutes by ultrasonic waves once every one part is added until all parts of powder are added at last, and uniformly stirring the resin composition to obtain the toughening phenolic adhesive.
(4) The obtained toughened phenolic adhesive and large grid glass cloth (surface density of 80 g/m) 2 A thickness of 0.10 mm) to prepare a resin film with a carrier, and the obtained product is the toughened phenolic resin film which can be used as a toughened strain transition layer;
(5) In order to represent the bonding capability between the strain transition layer and the metal cabin, the tensile and shearing strength data of the material are used for measuring indexes. The tensile shear test pieces were prepared from the material, and the tensile shear strength at room temperature and the tensile shear strength at 100℃were measured, and the results are shown in Table 1 below.
Example 6
(1) 1kg of absolute ethyl alcohol as a solvent was weighed into a first container, 2.5g of a dispersing agent (polyvinyl alcohol (CAS 9002-89-5, available from Shanghai Milin Biochemical technology Co., ltd., unless otherwise specified, the dispersing agent was used in the following examples) was added to the solvent and dissolved by ultrasonic dispersion, 500g of a phenolic adhesive (available from Heilongjiang petrochemical institute, average molecular weight of about 400, tensile shear strength at room temperature of 11.6 MPa) was weighed into the first container, and mixed to obtain a phenolic adhesive solution.
(2) 150g of carboxyl-terminated nitrile rubber powder (produced by Beijing chemical institute of petrochemical industry, china, average grain size of 50-100 nm) and 175g of modifier resorcinol are weighed into a second container, and are premixed for 0.5h by stirring paddles, so that uniform stirring is ensured, and subsequent dissolution and mixing are facilitated, and solid powder is obtained.
(3) And (3) dividing the mixed solid powder into 4 parts, sequentially adding the 4 parts into the phenolic adhesive solution prepared in the step (1), stirring and dispersing the mixture for 15 minutes by ultrasonic waves once every one part is added until all parts of powder are added at last, and uniformly stirring the resin composition to obtain the toughening phenolic adhesive.
(4) The obtained toughened phenolic adhesive and large grid glass cloth (surface density of 80 g/m) 2 A thickness of 0.10 mm) to prepare a resin film with a carrier, and the obtained product is the toughened phenolic resin film which can be used as a toughened strain transition layer;
(5) In order to represent the bonding capability between the strain transition layer and the metal cabin, the tensile and shearing strength data of the material are used for measuring indexes. The tensile shear test pieces were prepared from the material, and the tensile shear strength at room temperature and the tensile shear strength at 100℃were measured, and the results are shown in Table 1 below.
Example 7
(1) 1kg of absolute ethyl alcohol as a solvent was weighed into a first container, 2.5g of a dispersing agent (polyvinyl alcohol (CAS 9002-89-5, available from Shanghai Milin Biochemical technology Co., ltd., unless otherwise specified, the dispersing agent was used in the following examples) was added to the solvent and dissolved by ultrasonic dispersion, 500g of a phenolic adhesive (available from Heilongjiang petrochemical institute, average molecular weight of about 400, tensile shear strength at room temperature of 11.6 MPa) was weighed into the first container, and mixed to obtain a phenolic adhesive solution.
(2) 200g of carboxyl-terminated nitrile rubber powder (produced by Beijing chemical institute of petrochemical industry, china, average grain size of 50-100 nm) and 175g of modifier resorcinol are weighed into a second container, and are premixed for 0.5h by stirring paddles, so that uniform stirring is ensured, and subsequent dissolution and mixing are facilitated, and solid powder is obtained.
(3) The mixed solid powder is divided into 4 parts evenly, the 4 parts are added into the phenolic adhesive solution prepared in the step (1) in sequence, and the mixture is stirred and dispersed by ultrasonic waves for 15 minutes once every part is added until all parts of powder are added and stirred to obtain the mixture finally, but the mixture is difficult to stir evenly.
(4) The obtained mixture was fused with a large-mesh glass cloth (surface density 80g/m 2 Thickness of 0.10 mm) was produced as a supported resin film, but it was found that the resin film could not be produced in a process.
Table 1. The amounts of the partial raw materials used and the tensile shear strength of the materials produced (n=5) for each example and comparative example.
Note that: "/" indicates measured or not measured.
From the results of comparative example 1, it can be seen that the glass cloth significantly improves the room temperature tensile shear strength of the toughened phenolic resin film. From the results of examples 1 and 2, it can be seen that the modifier increases the temperature resistance rating of the adhesive, but does not change much in tensile strength at room temperature. From the results of comparative example 1 and examples 1 and 3, it can be seen that nitrile rubber can improve room temperature tensile shear strength with little effect on the adhesive temperature resistance rating. From the results of example 5, the room temperature tensile strength was slightly improved by increasing the amount of the carboxylated nitrile rubber, but it was not obvious that the tensile strength at 100℃was not further improved but slightly lowered. From the results of example 6, further increases in resorcinol use amount, no further significant improvement in room temperature tensile shear strength and 100℃tensile shear strength were observed. In examples 6 and 7, it was found that the amount of carboxyl terminated nitrile rubber used cannot be excessively large. Because the carboxyl-terminated nitrile rubber powder is an elastomer, the density is low, the volume ratio is large, and the carboxyl-terminated nitrile rubber powder is not easy to uniformly disperse in the mixture after the weight ratio is more than 30 parts by weight relative to 100 parts by weight of phenolic aldehyde adhesive; when the weight ratio is more than 40 with respect to 100 parts by weight of the phenolic adhesive, the preparation of the resin film (see standard deviation sigma of room temperature tensile shear strength) has not been realized in the art. In addition, from the above results, it is seen that the modifier (resorcinol) and the resin molecules undergo curing and crosslinking reaction to improve the temperature resistance of the cured product, and when the mass ratio is more than 30 with respect to 100 parts by weight of the phenolic adhesive, the excessive modifier does not participate in the chemical reaction, and the temperature resistance of the cured product is not improved any more.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (12)
1. A toughened resin film, characterized in that:
the resin film takes glass cloth as a carrier, and a toughening phenolic adhesive is loaded on the carrier;
the toughening phenolic adhesive is prepared from raw materials of phenolic adhesive, carboxyl-terminated nitrile rubber, a modifier and a dispersing agent, wherein the modifier is resorcinol; the mass ratio of the raw materials is as follows: 100 parts of phenolic adhesive, 10 to 30 parts of carboxyl terminated nitrile rubber, 10 to 30 parts of modifier and 0.2 to 0.8 part of dispersant;
the surface density of the glass cloth is 60 to 100g/m 2 The thickness of the glass cloth is 0.05 to 0.15mm.
2. The toughened resin film as claimed in claim 1, wherein the mass ratio of the raw materials is as follows: 100 parts of phenolic adhesive, 10 to 30 parts of carboxyl terminated nitrile rubber, 10 to 30 parts of modifier and 0.5 part of dispersing agent.
3. The toughened resin film as claimed in claim 1, wherein said phenolic adhesive has an average molecular weight of 300 to 500 and a room temperature tensile shear strength of 10 to 15MPa.
4. A toughened resin film as claimed in any one of claims 1 to 3, wherein said phenolic adhesive has an average molecular weight of 400 and a room temperature tensile shear strength of 11.6MPa.
5. The toughened resin film as claimed in claim 1, wherein said carboxyl terminated nitrile rubber is a nano carboxyl terminated nitrile rubber.
6. A toughened resin film as claimed in any one of claims 1 to 3, wherein said carboxyl terminated nitrile rubber has an average particle size of from 50nm to 100nm.
7. A toughened resin film as claimed in any one of claims 1 to 3, wherein said dispersing agent is selected from one or more of polyvinyl alcohol, polyethylene glycol, methylpentanol.
8. A toughened resin film as claimed in any one of claims 1 to 3, wherein said toughened phenolic adhesive is prepared by a process comprising the steps of:
(1) Adding ethanol which takes 1.5 to 2.5 times of the mass of the phenolic adhesive as a solvent into a first container, adding a dispersing agent into the solvent, dispersing and dissolving by using ultrasonic waves, and adding the phenolic adhesive into the first container for dissolving to obtain a phenolic adhesive solution;
(2) Putting the carboxyl-terminated nitrile rubber and the modifier into a second container and uniformly mixing to obtain solid powder;
(3) And (3) adding the solid powder prepared in the step (2) into the phenolic adhesive solution prepared in the step (1), and uniformly stirring to prepare the toughening phenolic adhesive.
9. The toughened resin film as claimed in claim 8, wherein in step (1), ethanol in an amount of 2 times the mass of the phenolic adhesive as a solvent is added to the first container, a dispersant is added to the solvent and dispersed and dissolved by ultrasonic waves, and then the phenolic adhesive is added to the first container and dissolved to obtain a phenolic adhesive solution.
10. The toughened resin film as claimed in claim 1, wherein said glass cloth has an areal density of 80g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or the glass cloth has a thickness of 0.1mm.
11. A method of producing the toughened resin film of any of claims 1 to 10, characterized by:
and loading the toughening phenolic adhesive on the glass cloth serving as a carrier by using a hot melting method to obtain the toughening resin film.
12. Use of the toughened resin film of any of claims 1 to 10 or the toughened resin film made by the method of claim 11 as a toughened strain transition layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111341953.0A CN113930199B (en) | 2021-11-12 | 2021-11-12 | Toughening phenolic adhesive and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111341953.0A CN113930199B (en) | 2021-11-12 | 2021-11-12 | Toughening phenolic adhesive and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113930199A CN113930199A (en) | 2022-01-14 |
| CN113930199B true CN113930199B (en) | 2024-02-20 |
Family
ID=79286526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111341953.0A Active CN113930199B (en) | 2021-11-12 | 2021-11-12 | Toughening phenolic adhesive and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113930199B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11140404A (en) * | 1997-11-13 | 1999-05-25 | Unitta Co Ltd | Adhesive, composite of rubber and canvas, and timing belt |
| JP2012197376A (en) * | 2011-03-22 | 2012-10-18 | Sumitomo Bakelite Co Ltd | Phenol resin molding material |
| CN104877583A (en) * | 2015-06-16 | 2015-09-02 | 黑龙江省科学院石油化学研究院 | High-temperature-resistant phenolic unsupported structural adhesive film and preparation method thereof |
| CN105882077A (en) * | 2016-04-27 | 2016-08-24 | 航天材料及工艺研究所 | Method using coating technology to prepare solution-method phenolic aldehyde prepreg |
| CN108485555A (en) * | 2018-04-17 | 2018-09-04 | 武汉理工大学 | A kind of high temperature resistance phenolic aldehyde carrier adhesive and preparation method thereof |
| CN109971120A (en) * | 2019-04-08 | 2019-07-05 | 航天特种材料及工艺技术研究所 | A kind of toughening type phenolic resin and preparation method thereof |
| CN110001092A (en) * | 2019-05-16 | 2019-07-12 | 航天特种材料及工艺技术研究所 | A kind of phenolic resin preimpregnation material and metalwork integral formation method |
| CN112724439A (en) * | 2020-11-23 | 2021-04-30 | 航天特种材料及工艺技术研究所 | Light heat-insulating micro-ablation prepreg and preparation method thereof |
-
2021
- 2021-11-12 CN CN202111341953.0A patent/CN113930199B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11140404A (en) * | 1997-11-13 | 1999-05-25 | Unitta Co Ltd | Adhesive, composite of rubber and canvas, and timing belt |
| JP2012197376A (en) * | 2011-03-22 | 2012-10-18 | Sumitomo Bakelite Co Ltd | Phenol resin molding material |
| CN104877583A (en) * | 2015-06-16 | 2015-09-02 | 黑龙江省科学院石油化学研究院 | High-temperature-resistant phenolic unsupported structural adhesive film and preparation method thereof |
| CN105882077A (en) * | 2016-04-27 | 2016-08-24 | 航天材料及工艺研究所 | Method using coating technology to prepare solution-method phenolic aldehyde prepreg |
| CN108485555A (en) * | 2018-04-17 | 2018-09-04 | 武汉理工大学 | A kind of high temperature resistance phenolic aldehyde carrier adhesive and preparation method thereof |
| CN109971120A (en) * | 2019-04-08 | 2019-07-05 | 航天特种材料及工艺技术研究所 | A kind of toughening type phenolic resin and preparation method thereof |
| CN110001092A (en) * | 2019-05-16 | 2019-07-12 | 航天特种材料及工艺技术研究所 | A kind of phenolic resin preimpregnation material and metalwork integral formation method |
| CN112724439A (en) * | 2020-11-23 | 2021-04-30 | 航天特种材料及工艺技术研究所 | Light heat-insulating micro-ablation prepreg and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 一种高弹性环氧基胶粘剂材料的制备;冯浩等;《中国胶粘剂》;20181130(第11期);全文 * |
| 丁腈橡胶改性酚醛树脂/玻纤布复合预浸料的研制;聂锡铭等;《工程塑料应用》;20190310(第03期);全文 * |
| 柴春鹏等.酚醛树脂.《高分子合成材料学》.北京理工大学出版社,2019, * |
| 耐高温硼改性酚醛胶粘剂的制备及性能研究;张春爱等;《热固性树脂》;20160930(第05期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113930199A (en) | 2022-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103030921B (en) | Clutch facing without rubber winding and preparation method thereof | |
| CN102936466B (en) | Modified bisphthalonitrile resin structure glue film and preparation method thereof | |
| CN103242767A (en) | High-temperature-resistant bismaleimide resin carrier structure adhesive film and preparation method thereof | |
| CN105176081A (en) | Preparation method for flame-retardant heat-resistant antenna radome base material | |
| CN103965590A (en) | Synergistically toughened epoxy resin composite material and preparation method thereof | |
| CN112048247B (en) | Bismaleimide/cyanate ester foamed adhesive film, and preparation method and application thereof | |
| CN112608708A (en) | Polyurethane heat-conducting insulating adhesive and preparation method thereof | |
| Li et al. | High-performance quartz fiber/polysilazane and epoxy-modified cyanate ester microwave-transparent composites | |
| CN112048118A (en) | Ultraviolet crosslinking-based flame-retardant high-strength polyethylene material and preparation method thereof | |
| CN114103305B (en) | high-Tg high-heat-conductivity metal-based copper-clad plate and processing technology thereof | |
| CN114605697A (en) | Low-density high-strength buoyancy material and preparation method thereof | |
| CN113930199B (en) | Toughening phenolic adhesive and preparation method and application thereof | |
| CN106047271B (en) | A kind of low dielectric cyanate ester adhesive and preparation method thereof | |
| CN111376571A (en) | Preparation method of surface super-hydrophobic composite material | |
| CN112662357A (en) | Epoxy foaming structure adhesive film resisting 177 ℃ hot oxygen for 3000 hours and preparation method thereof | |
| CN114752314B (en) | High-durability high-temperature cured epoxy structural adhesive film and preparation method thereof | |
| CN111548760A (en) | Epoxy resin adhesive and preparation method thereof | |
| CN109971120B (en) | Toughened phenolic resin and preparation method thereof | |
| CN113801473B (en) | Wave-absorbing bismaleimide resin, wave-absorbing bismaleimide resin composite material and preparation method thereof | |
| CN114687246B (en) | Epoxy-based silicone resin sizing agent, mica plate and preparation method and application thereof | |
| CN113801437B (en) | Wave-absorbing epoxy resin, wave-absorbing epoxy resin composite material and preparation method thereof | |
| CN113337077B (en) | High-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with isolation structure and preparation method and application thereof | |
| CN112111095B (en) | Composite wax powder material suitable for selective laser sintering process | |
| WO2018061516A1 (en) | Fiber-reinforced plastic molding material, method for producing same, and molded product | |
| JP6944804B2 (en) | Manufacturing method of prepreg for fiber reinforced plastic molding |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |