CN116903861B - Synthesis method of high ammonia value silicone oil, organic silicon/epoxy adhesive film, preparation method of organic silicon/epoxy adhesive film and bendable laminated board - Google Patents

Synthesis method of high ammonia value silicone oil, organic silicon/epoxy adhesive film, preparation method of organic silicon/epoxy adhesive film and bendable laminated board Download PDF

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CN116903861B
CN116903861B CN202311168941.1A CN202311168941A CN116903861B CN 116903861 B CN116903861 B CN 116903861B CN 202311168941 A CN202311168941 A CN 202311168941A CN 116903861 B CN116903861 B CN 116903861B
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epoxy
film
silicone oil
adhesive film
organic silicon
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CN116903861A (en
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吴谦
姚超凡
吴一琪
尤涛
李树茂
刘丽
黄玉东
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Harbin Institute of Technology
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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    • 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
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • 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
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/42—Alternating layers, e.g. ABAB(C), AABBAABB(C)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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    • B32B2262/0261—Polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
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    • C08K2003/323—Ammonium polyphosphate
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Abstract

A synthetic method of high ammonia value silicone oil, an organic silicon/epoxy adhesive film, a preparation method thereof and a bendable laminated board belong to the technical field of preparation of epoxy resin adhesive films. The specific scheme is as follows: the raw materials of the low-density and low-heat-conduction flame-retardant organic silicon/epoxy adhesive film comprise the following components in parts by weight: 30-50 parts of epoxy resin, 1-4 parts of coupling agent, 10-30 parts of silicon dioxide aerogel powder, 40-100 parts of flame retardant and 2-8 parts of high ammonia value silicone oil. The prepared epoxy adhesive film is used for preparing a composite material plate, the composite material plate has excellent flame retardance and heat insulation performance, and the composite material bent by more than 90 degrees is not damaged.

Description

Synthesis method of high ammonia value silicone oil, organic silicon/epoxy adhesive film, preparation method of organic silicon/epoxy adhesive film and bendable laminated board
Technical Field
The invention belongs to the technical field of preparation of epoxy resin adhesive films, and particularly relates to a synthetic method of high ammonia value silicone oil, a low-density and low-heat-conduction flame-retardant organic silicon/epoxy adhesive film, a preparation method thereof and a bendable laminated board.
Background
With the rapid development of aerospace, automobile industry and electronic communication technology, not only are higher requirements on the strength, high temperature resistance and other basic performances of materials provided, but also more requirements on the density, heat insulation, flame retardance, flexibility and other functionalities of the materials are provided. Epoxy resin is used as a thermosetting resin in various industries, and an epoxy adhesive film is a single-component adhesive film, and after reaching a certain temperature, amino silicone oil and the resin are preliminarily crosslinked to play roles of adhesion, protection and the like. Along with the development of technology, higher requirements are put forward on the functions of the epoxy adhesive film, and the multifunctional adhesive film has very wide application prospects in various fields of electronics, communication, automobiles, spaceflight, machinery, ships, rail transit, wind power generation, buildings and the like, and is favored by the industry.
In recent years, attention to an epoxy adhesive film and a composite material thereof has been focused on performances such as high bonding strength, high/low temperature resistance, high mechanical properties and the like, and the epoxy resin composite material has few reports on performances such as low density, high-efficiency heat insulation, flame retardance, bending property and the like. With the rapid development of aerospace, automobile industry and electronic communication technology, the demand for the epoxy resin composite material with low density, high-efficiency heat insulation, flame retardance, bending property and the like is more urgent. At present, no prior art exists for preparing silicone/epoxy films that have properties of low density, high efficiency thermal insulation, flame retardance, and flexibility at the same time.
In the prior art, the curing agents of the epoxy resin are mainly aliphatic amine and aromatic amine, and the curing agents have poor flame retardant property and poor flame retardant property of the cured epoxy resin.
Disclosure of Invention
In order to improve the flame retardance and the flexibility of the epoxy resin composite material and reduce the density thereof, the invention provides a synthetic method of high-ammonia-value silicone oil, a low-density and low-heat-conduction flame-retardant organic silicon/epoxy adhesive film, a preparation method thereof and a bendable laminated board.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a synthetic method of high ammonia value silicone oil comprises the following steps:
under the protection of nitrogen, adding 1, 3-bis (aminopropyl) tetramethyl disiloxane and N- (beta-aminoethyl-gamma-aminopropyl) methyldiethoxysilane into a reaction container, uniformly mixing to obtain a mixture A, dropwise adding deionized water into the mixture A, and heating to 75 ℃ after dropwise adding, and carrying out reflux hydrolysis-condensation reaction for 8-16 hours; wherein the molar ratio of the 1, 3-di (aminopropyl) tetramethyl disiloxane, the N- (beta-aminoethyl-gamma-aminopropyl) methyl diethoxy silane and the deionized water is 1:10-100:20-200;
and step two, after the reaction is finished, heating to 110-130 ℃, distilling under reduced pressure to remove ethanol produced by the hydrolysis reaction and dropwise adding deionized water until no liquid is distilled, keeping the vacuum degree smaller than-0.08 MPa, continuing to react for 2-4 hours, heating to 150 ℃ and keeping the vacuum degree smaller than-0.08 MPa, reacting for 2-4 hours, and naturally cooling to room temperature after the reaction is finished, thus obtaining the high ammonia value silicone oil.
Further, the amino value content of the high-ammonia-value silicone oil is 8.6-9.3 mmol/g, and the molecular structure diagram is shown as follows:
wherein n is more than or equal to 10 and less than or equal to 100.
The organic silicon/epoxy adhesive film comprises the following raw materials in parts by weight:
30-50 parts of epoxy resin;
1-4 parts of a coupling agent;
10-30 parts of silicon dioxide aerogel powder;
40-100 parts of flame retardant;
2-8 parts of high ammonia value silicone oil;
the high ammonia value silicone oil is synthesized by the synthesis method.
Further, the epoxy resin is polyester epoxy resin, the equivalent of the epoxy value is 0.1-0.3, and the molecular structure is shown in the following schematic diagram:
。
further, the coupling agent comprises one or more of 2- (3, 4-epoxycyclohexane) ethyl trimethoxysilane, 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyldimethoxy silane and 3-glycidoxypropyl methyldiethoxy silane; the flame retardant comprises one or more combinations of polyphosphoric acid, ammonium polyphosphate, melamine polyphosphate, and melamine cyanurate.
Further, the silica aerogel powder has a particle size of 10-50 μm and a specific surface area of 500-900g/m 2 。
The preparation method of the organic silicon/epoxy adhesive film comprises the following steps:
step 1, adding epoxy resin, a coupling agent, silica aerogel powder and a flame retardant into a kneading kettle, stirring, controlling the temperature to be 100-120 ℃ for reaction for 2-4 hours, vacuumizing the kneading kettle to be below-0.08 MPa, maintaining vacuum, and continuously heating at 100-120 ℃ for 0.5-2 hours to remove small molecules to obtain an intermediate;
step 2, cooling the intermediate obtained in the step 1 to 80 ℃, adding high ammonia value silicone oil into a kneading kettle, stirring, and pre-curing for 0.5-2 hours to obtain a sizing material;
and 3, heating the sizing material obtained in the step 2 for 0.5-2 hours at the temperature of 60-80 ℃, hot-pressing the sizing material into a film with a certain thickness on a film machine with the roller temperature of 70-90 ℃, and compositing the film with a protective film to obtain the organosilicon/epoxy film.
The utility model provides a flexible laminate, includes a plurality of layers organosilicon epoxy glued membrane and a plurality of layer fiber cloth, a plurality of layers organosilicon epoxy glued membrane and a plurality of layer fiber cloth interval and lamination set up and obtain the prefabrication body, wherein the upper and lower two surfaces of prefabrication body are organosilicon epoxy glued membrane, prepare the composite board through hot pressing with the prefabrication body, can buckle the laminate.
Further, the fiber cloth comprises one or more of quartz fiber cloth, hollow quartz fiber cloth, high silica fiber cloth, glass fiber cloth, aramid fiber cloth, PBO fiber cloth and super-molecular weight polyethylene fiber cloth.
Further, the hot pressing temperature is 150-180 ℃, the hot pressing pressure is 1-5MPa, and the hot pressing time is 0.5-2 hours.
Compared with the prior art, the invention has the beneficial effects that:
the high-ammonia-value silicone oil is used as a curing agent, active hydrogen is provided by the high-ammonia-value silicone oil to crosslink epoxy groups, meanwhile, si-O-Si contained in the high-ammonia-value silicone oil has excellent high temperature resistance and flame retardance, oxidation-resistant and incombustible silicon dioxide is generated by high-temperature decomposition of the high-ammonia-value silicone oil, the high-ammonia-value silicone oil can effectively inhibit the combustion of the resin, the flame retardance of the epoxy resin can be further improved by adding the high-ammonia-value silicone oil, meanwhile, the Si-O-Si structure of a main chain of the high-ammonia-value silicone oil is spiral, and the bond angle can be changed between 140 degrees and 180 degrees, so that the high-ammonia-value silicone oil is very soft. Therefore, in the preparation process of the low-density low-heat-conduction flame-retardant organic silicon/epoxy adhesive film, the addition of the high-ammonia-value silicone oil not only improves the flame retardant property of the epoxy resin, but also ensures that the composite material plate has more excellent flexibility. The prepared epoxy adhesive film is used for preparing a composite material plate, the composite material plate has excellent flame retardance and heat insulation performance, and the composite material bent by more than 90 degrees is not damaged. In addition, the synthesis of the high-ammonia-value silicone oil only adopts 1, 3-di (aminopropyl) tetramethyl disiloxane and N- (beta-aminoethyl-gamma-aminopropyl) methyl diethoxy silane as raw materials, no catalyst is added, and the prepared amino silicone oil has high purity and no impurities such as metal particles. The high ammonia value silicone oil synthesis and preparation process provided by the invention has the advantages of simplicity in operation, high purity of the amino silicone oil, controllable viscosity and amine value and the like, and is suitable for industrial production.
Drawings
FIG. 1 is a graph showing the results of a high ammonia value silicone oil gel chromatography test prepared in example 1;
FIG. 2 is a high amino silicone oil prepared in example 1 1 H nuclear magnetic spectrum.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and examples, and it is apparent that the described examples are only some, but not all, of the examples of the invention, and all other examples obtained by those skilled in the art without making any inventive effort are within the scope of the present invention.
Example 1
The synthetic method of the high ammonia value silicone oil comprises the following steps:
1, 3-di (aminopropyl) tetramethyl disiloxane, N- (beta-aminoethyl-gamma-aminopropyl) methyldiethoxysilane and deionized water in a molar ratio of 1:10:20 are weighed;
under the protection of nitrogen, adding 1, 3-di (aminopropyl) tetramethyl disiloxane and N- (beta-aminoethyl-gamma-aminopropyl) methyl diethoxy silane weighed in the step I into a reaction vessel, uniformly mixing to obtain a mixture A, dropwise adding weighed deionized water into the mixture A, and heating to 75 ℃ after the dropwise adding is completed, and carrying out reflux hydrolysis-condensation reaction for 12 hours;
(III) after the reaction is finished, heating to 110 ℃, distilling under reduced pressure to remove ethanol produced by hydrolysis reaction and dropwise adding deionized water until no liquid is distilled, keeping the vacuum degree smaller than-0.08 MPa, continuing to react for 2.5 hours, heating to 150 ℃ and keeping the vacuum degree smaller than-0.08 MPa, reacting for 2 hours, naturally cooling to room temperature after the reaction is finished, and obtaining high-ammonia-value silicone oil, wherein gel chromatography test junction of the high-ammonia-value silicone oil is obtainedAs a result of the fact that as shown in figure 1, 1 the H test results are shown in fig. 2.
The preparation method of the low-density and low-heat-conduction flame-retardant epoxy adhesive film and the preparation method of the bendable laminated board comprise the following steps:
(1) 40 parts of polyester epoxy resin with an epoxy value of 0.21, 1 part of 3-glycidoxypropyl triethoxysilane, 1 part of 3-glycidoxypropyl methyl diethoxysilane, 15 parts of polyester epoxy resin with a particle size of 35 microns and a density of 0.18 g/cm are weighed according to parts by weight 3 Specific surface area of 580g/m 2 30 parts of polyphosphoric acid, 35 parts of melamine cyanurate and 4.8 parts of high ammonia silicone oil.
(2) Adding the epoxy resin, the coupling agent, the silica aerogel powder and the flame retardant which are weighed in the step (1) into a kneading kettle, stirring, controlling the temperature to be 100 ℃ for reacting for 4 hours, vacuumizing the kneading machine to-0.09 MPa, maintaining vacuum, continuously heating and stirring at 120 ℃ for 0.5 hour, removing small molecules to obtain a mixture B, and cooling the mixture B to 80 ℃.
(3) And (3) adding the high ammonia value silicone oil weighed in the step (1) into a kneading kettle, stirring and uniformly mixing with the mixture B, and then pre-solidifying at 80 ℃ for 1 hour to obtain a mixture C.
(4) And (3) heating the mixture C obtained in the step (3) for 1 hour at the temperature of 80 ℃, hot-pressing the mixture C into a film with the thickness of 0.25mm on a film machine with the roller temperature of 90 ℃, and compositing the film with a protective film to obtain the low-density flame-retardant epoxy resin film.
(5) And (3) removing the protective film from the adhesive film, and paving one layer of adhesive film and one layer of fiber cloth with the thickness of 0.2mm with the quartz fiber cloth, wherein 10 layers of adhesive films and 8 layers of fiber cloth are paved to obtain the preform.
(6) And (3) placing the preform in a hot press with the temperature of 170 ℃, applying the pressure of 2MPa, and hot-pressing for 0.5 hour to obtain the quartz fiber reinforced organic silicon/epoxy composite board, namely the bendable laminated board.
Example 2
The synthetic method of the high ammonia value silicone oil comprises the following steps:
1, 3-di (aminopropyl) tetramethyl disiloxane, N- (beta-aminoethyl-gamma-aminopropyl) methyldiethoxysilane and deionized water in a molar ratio of 1:20:35 are weighed;
and (II) adding the 1, 3-di (aminopropyl) tetramethyl disiloxane and the N- (beta-aminoethyl-gamma-aminopropyl) methyldiethoxysilane weighed in the step I into a reaction vessel under the protection of nitrogen, uniformly mixing to obtain a mixture A, dropwise adding the weighed deionized water into the mixture A, and heating to 75 ℃ after the dropwise adding is finished, and carrying out reflux hydrolysis-condensation reaction for 16 hours.
And (III) heating to 110 ℃ after the reaction is finished, distilling under reduced pressure to remove ethanol produced by the hydrolysis reaction and dropwise adding deionized water until no liquid is distilled, keeping the vacuum degree smaller than-0.08 MPa for continuous reaction for 3 hours, heating to 150 ℃ and keeping the vacuum degree smaller than-0.08 MPa for reaction for 3 hours, and naturally cooling to room temperature after the reaction is finished to obtain the high ammonia value silicone oil.
The preparation method of the low-density low-heat-conduction flame-retardant epoxy adhesive film and the preparation method of the bendable laminated board provided by the embodiment comprise the following steps:
(1) 40 parts by weight of a polyester epoxy resin having an epoxy value of 0.25, 2 parts by weight of 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane, 20 parts by weight of a polyester epoxy resin having a particle diameter of 40 μm and a density of 0.15 g/cm are weighed 3 Specific surface area of 650g/m 2 60 parts of melamine polyphosphate and 5.1 parts of high ammonia silicone oil.
(2) Adding the epoxy resin, the coupling agent, the silica aerogel powder and the flame retardant which are weighed in the step (1) into a kneading kettle, stirring, controlling the temperature to be 90 ℃ for reaction for 4 hours, vacuumizing the kneading machine to-0.09 MPa, maintaining vacuum, continuously heating and stirring at 100 ℃ for 1.5 hours, removing small molecules to obtain a mixture B, and cooling the mixture B to 80 ℃.
(3) And (3) adding the high ammonia value silicone oil weighed in the step (1) into a kneading kettle, stirring and uniformly mixing with the mixture B, and then pre-solidifying at 80 ℃ for 1 hour to obtain a mixture C.
(4) And (3) heating the mixture C obtained in the step (3) for 1 hour at 70 ℃, hot-pressing the mixture C into a film with the thickness of 0.30mm on a film machine with the roller temperature of 70 ℃, and compositing the film with a protective film to obtain the low-density flame-retardant epoxy resin film.
(5) And (3) removing the protective film from the adhesive film, and paving one layer of adhesive film and one layer of fiber cloth with the thickness of 0.28mm with the aramid fiber cloth, wherein the 18 layers of adhesive films and the 16 layers of fiber cloth are paved to obtain the preform.
(6) And (3) placing the preform in a hot press with the temperature of 160 ℃, applying the pressure of 2MPa, and hot-pressing for 1.5 hours to obtain the aramid fiber reinforced organic silicon/epoxy composite board, thus obtaining the bendable laminated board.
Example 3
The synthetic method of the high ammonia value silicone oil comprises the following steps:
1, 3-di (aminopropyl) tetramethyl disiloxane, N- (beta-aminoethyl-gamma-aminopropyl) methyldiethoxysilane and deionized water in a molar ratio of 1:50:100 were weighed.
Adding 1, 3-di (aminopropyl) tetramethyl disiloxane and N- (beta-aminoethyl-gamma-aminopropyl) methyldiethoxysilane weighed in the step I into a reaction vessel under the protection of nitrogen, uniformly mixing to obtain a mixture A, dripping the weighed deionized water into the mixture A, and heating to 75 ℃ after the dripping is finished for reflux hydrolysis-condensation reaction for 18 hours;
and (III) heating to 110 ℃ after the reaction is finished, distilling under reduced pressure to remove ethanol produced by the hydrolysis reaction and dropwise adding deionized water until no liquid is distilled, keeping the vacuum degree smaller than-0.08 MPa, continuing the reaction for 2 hours, heating to 150 ℃ and keeping the vacuum degree smaller than-0.08 MPa, reacting for 3.5 hours, and naturally cooling to room temperature after the reaction is finished to obtain the high ammonia value silicone oil.
The embodiment provides a preparation method of a low-density and low-heat-conduction flame-retardant epoxy adhesive film and a preparation method of a bendable laminated board, which comprises the following steps:
(1) 35 parts by weight of polyester epoxy resin with an epoxy value of 0.2, 1 part of 2- (3, 4-epoxycyclohexane) ethyl trimethoxysilane, 1 part of 3-glycidoxypropyl methyl diethoxy silane, 1 part of 3-glycidoxypropyl triethoxy silane and 18 parts of polyester epoxy resin with a particle size of 40 microns and a density of 0.25 g/cm are weighed 3 The specific surface area is 720g/m 2 40 parts of ammonium polyphosphate, 40 parts of melamine and 4.2 parts of high-ammonia-value silicone oil。
(2) Adding the epoxy resin, the coupling agent, the silica aerogel powder and the flame retardant which are weighed in the step (1) into a kneading kettle, stirring, controlling the temperature to be 100 ℃ for reacting for 4 hours, vacuumizing the kneading machine to-0.1 MPa, maintaining vacuum, continuously heating and stirring at 120 ℃ for 1 hour, removing small molecules, obtaining a mixture B, and cooling the mixture B to 80 ℃.
(3) And (3) adding the high ammonia value silicone oil weighed in the step (1) into a kneading kettle, stirring and uniformly mixing with the mixture B, and then pre-solidifying at 80 ℃ for 1 hour to obtain a mixture C.
(4) And (3) heating the mixture C obtained in the step (3) for 1.5 hours at the temperature of 80 ℃, hot-pressing the mixture C into a film with the thickness of 0.2mm on a film machine with the roller temperature of 80 ℃, and compositing the film with a protective film to obtain the low-density flame-retardant epoxy resin film.
(5) And (3) tearing off the protective film from the adhesive film, and paving the adhesive film and the PBO fabric with the thickness of 0.18mm by one layer of adhesive film and one layer of fiber fabric, wherein 16 layers of adhesive films and 14 layers of fiber fabrics are paved to obtain the preform.
(6) And (3) placing the preform in a hot press with the temperature of 160 ℃, applying the pressure of 5MPa, and hot-pressing for 1 hour to obtain the BPO fiber reinforced organic silicon/epoxy composite board, namely the bending laminated board.
Example 4
The synthetic method of the high ammonia value silicone oil comprises the following steps:
1, 3-di (aminopropyl) tetramethyl disiloxane, N- (beta-aminoethyl-gamma-aminopropyl) methyldiethoxysilane and deionized water in a molar ratio of 1:80:120 were weighed.
And (II) adding the 1, 3-di (aminopropyl) tetramethyl disiloxane and the N- (beta-aminoethyl-gamma-aminopropyl) methyldiethoxysilane weighed in the step I into a reaction vessel under the protection of nitrogen, uniformly mixing to obtain a mixture A, dropwise adding the weighed deionized water into the mixture A, and heating to 75 ℃ after the dropwise adding is finished, and carrying out reflux hydrolysis-condensation reaction for 20 hours.
And (III) heating to 110 ℃ after the reaction is finished, distilling under reduced pressure to remove ethanol produced by the hydrolysis reaction and dropwise adding deionized water until no liquid is distilled, keeping the vacuum degree smaller than-0.08 MPa for continuous reaction for 3 hours, heating to 150 ℃ and keeping the vacuum degree smaller than-0.08 MPa for reaction for 4 hours, and naturally cooling to room temperature after the reaction is finished to obtain the high ammonia value silicone oil.
The embodiment provides a preparation method of a low-density and low-heat-conduction flame-retardant epoxy adhesive film and a preparation method of a bendable laminated board, which comprises the following steps:
(1) 30 parts by weight of polyester epoxy resin with an epoxy value of 0.1, 1 part of 3-glycidoxypropyl triethoxysilane, 1 part of 3-glycidoxypropyl methyldiethoxysilane, 27 parts of polyester epoxy resin with a particle size of 45 micrometers and a density of 0.15 g/cm are weighed 3 60 parts of melamine cyanurate and 2.3 parts of silicone oil with high ammonia value.
(2) Adding the epoxy resin, the coupling agent, the silica aerogel powder and the flame retardant which are weighed in the step (1) into a kneading kettle, stirring, controlling the temperature to be 100 ℃ for reacting for 4 hours, vacuumizing the kneading machine to-0.1 MPa, maintaining vacuum, continuously heating and stirring at 110 ℃ for 1.5 hours, removing small molecules to obtain a mixture B, and cooling the mixture B to 80 ℃.
(3) And (3) adding the high ammonia value silicone oil weighed in the step (1) into a kneading kettle, stirring and uniformly mixing with the mixture B, and then pre-solidifying at 80 ℃ for 1 hour to obtain a mixture C.
(4) And (3) heating the mixture C obtained in the step (3) for 0.5 hour at the temperature of 70 ℃, hot-pressing the mixture C into a film with the thickness of 0.2mm on a film machine with the roller temperature of 80 ℃, and compositing the film with a protective film to obtain the low-density flame-retardant epoxy resin film.
(5) Removing the protective film from the adhesive film, and paving the adhesive film with a layer of adhesive film and a layer of fiber cloth of hollow quartz fiber cloth with the thickness of 0.18mm, wherein 14 layers of adhesive films and 12 layers of fiber cloth are paved to obtain a preform;
(6) And (3) placing the preform in a hot press with the temperature of 180 ℃, applying the pressure of 2.5MPa, and hot-pressing for 0.5 hour to obtain the quartz fiber reinforced organic silicon/epoxy composite board, namely the bendable laminated board.
Example 5
The synthetic method of the high ammonia value silicone oil comprises the following steps:
1, 3-di (aminopropyl) tetramethyl disiloxane, N- (beta-aminoethyl-gamma-aminopropyl) methyldiethoxysilane and deionized water in a molar ratio of 1:100:180 were weighed.
Adding 1, 3-di (aminopropyl) tetramethyl disiloxane and N- (beta-aminoethyl-gamma-aminopropyl) methyldiethoxysilane weighed in the step I into a reaction vessel under the protection of nitrogen, uniformly mixing to obtain a mixture A, dropwise adding deionized water into the mixture A, and heating to 75 ℃ after the dropwise adding is finished to carry out reflux hydrolysis-condensation reaction for 24 hours;
and (III) heating to 110 ℃ after the reaction is finished, distilling under reduced pressure to remove ethanol produced by the hydrolysis reaction and dropwise adding deionized water until no liquid is distilled, keeping the vacuum degree smaller than-0.08 MPa, continuing the reaction for 4 hours, heating to 150 ℃ and keeping the vacuum degree smaller than-0.08 MPa, reacting for 4 hours, and naturally cooling to room temperature after the reaction is finished to obtain the high ammonia value silicone oil.
The preparation method of the low-density low-heat-conduction flame-retardant epoxy adhesive film and the preparation method of the bendable laminated board provided by the embodiment comprise the following steps:
(1) 50 parts by weight of polyester epoxy resin with an epoxy value of 0.15, 0.5 part of 3-glycidoxypropyl triethoxysilane, 1 part of 3-glycidoxypropyl methyldiethoxysilane, 10 parts of polyester epoxy resin with a diameter of 30 micrometers and a density of 0.30g/cm are weighed 3 Specific surface area of 800g/m 2 20 parts of polyphosphoric acid, 25 parts of ammonium polyphosphate, 30 parts of melamine cyanurate and 4.5 parts of high ammonia silicone oil.
(2) Adding the epoxy resin, the coupling agent, the silica aerogel powder and the flame retardant which are weighed in the step (1) into a kneading kettle, stirring, controlling the temperature to be 100 ℃ for reacting for 4 hours, vacuumizing the kneading machine to-0.1 MPa, maintaining vacuum, continuously heating and stirring at 100 ℃ for 1 hour to remove small molecules, obtaining a mixture B, and cooling the mixture B to 80 ℃.
(3) And (3) adding the high ammonia value silicone oil weighed in the step (1) into a kneading kettle, stirring and uniformly mixing with the mixture B, and then pre-solidifying at 80 ℃ for 1 hour to obtain a mixture C.
(4) And (3) heating the mixture C obtained in the step (3) for 0.5 hour at the temperature of 80 ℃, hot-pressing the mixture C into a film with the thickness of 0.25mm on a film machine with the roller temperature of 90 ℃, and compositing the film with a protective film to obtain the low-density flame-retardant epoxy resin film.
(5) And (3) after tearing off the protective film, paving the protective film with hollow stone fiber cloth with the thickness of 0.2mm and PBO fiber cloth with the thickness of 0.2mm, and paving one layer of adhesive film-one layer of hollow quartz fiber cloth-one layer of adhesive film-one layer of PBO fiber cloth circularly, wherein a preform is obtained by paving 12 layers of adhesive films and 10 layers of fiber cloth.
(6) And (3) placing the preform in a hot press with the temperature of 180 ℃, applying the pressure of 1.5MPa, and hot-pressing for 1.5 hours to obtain the quartz fiber and PBO reinforced organic silicon/epoxy composite board, namely the bendable laminated board.
The density of the epoxy films prepared in examples 1 to 5 and the density, thermal conductivity, tensile strength, bending angle, and flame retardancy of the composite board (bendable laminate) were tested, and the test results are shown in table 1.
TABLE 1 Performance parameters of epoxy films and composite panels
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.

Claims (9)

1. An organosilicon/epoxy adhesive film, characterized in that: the raw materials of the organic silicon/epoxy adhesive film comprise the following components in parts by weight:
the synthesis method of the high ammonia value silicone oil comprises the following steps:
under the protection of nitrogen, adding 1, 3-bis (aminopropyl) tetramethyl disiloxane and N- (beta-aminoethyl-gamma-aminopropyl) methyldiethoxysilane into a reaction vessel, uniformly mixing to obtain a mixture A, dropwise adding deionized water into the mixture A, and heating to 75 ℃ after the dropwise adding is finished, and carrying out reflux hydrolysis-condensation reaction for 8-16 hours; wherein the mol ratio of the 1, 3-di (aminopropyl) tetramethyl disiloxane, the N- (beta-aminoethyl-gamma-aminopropyl) methyl diethoxy silane and the deionized water is 1:10-100:20-200;
and step two, after the reaction is finished, heating to 110-130 ℃, distilling under reduced pressure to remove ethanol produced by the hydrolysis reaction and dropwise adding deionized water until no liquid is distilled, keeping the vacuum degree smaller than-0.08 MPa, continuing to react for 2-4 hours, heating to 150 ℃ and keeping the vacuum degree smaller than-0.08 MPa, reacting for 2-4 hours, and naturally cooling to room temperature after the reaction is finished, thus obtaining the high ammonia value silicone oil.
2. The silicone/epoxy film of claim 1, wherein: the amino value content of the high-ammonia-value silicone oil is 8.6-9.3 mmol/g, and the molecular structure schematic diagram is shown in the following figure:
wherein n is more than or equal to 10 and less than or equal to 100.
3. The silicone/epoxy film of claim 1, wherein: the epoxy resin is polyester epoxy resin, the equivalent of the epoxy value is 0.1-0.3, and the molecular structure diagram is shown in the following diagram:
4. the silicone/epoxy film of claim 1, wherein: the coupling agent comprises one or more of 2- (3, 4-epoxycyclohexane) ethyl trimethoxysilane, 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyldimethoxy silane and 3-glycidoxypropyl methyldiethoxy silane; the flame retardant comprises one or more combinations of polyphosphoric acid, ammonium polyphosphate, melamine polyphosphate, and melamine cyanurate.
5. The silicone/epoxy film of claim 1, wherein: the particle size of the silica aerogel powder is 10-50 microns, and the specific surface area is 500-900g/m 2 。
6. A method for preparing the organic silicon/epoxy adhesive film according to any one of claims 1 to 5, which is characterized in that: the method comprises the following steps:
step 1, adding epoxy resin, a coupling agent, silica aerogel powder and a flame retardant into a kneading kettle, stirring, controlling the temperature to be 100-120 ℃ for reaction for 2-4 hours, vacuumizing the kneading kettle to be below-0.08 MPa, maintaining vacuum, and continuously heating at 100-120 ℃ for 0.5-2 hours to remove small molecules to obtain an intermediate;
step 2, cooling the intermediate obtained in the step 1 to 80 ℃, adding high ammonia value silicone oil into a kneading kettle, stirring, and pre-curing for 0.5-2 hours to obtain a sizing material;
and 3, heating the sizing material obtained in the step 2 for 0.5-2 hours at the temperature of 60-80 ℃, hot-pressing the sizing material into a film with a certain thickness on a film machine with the roller temperature of 70-90 ℃, and compositing the film with a protective film to obtain the organosilicon/epoxy film.
7. A bendable laminate, characterized in that: the method comprises the steps of preparing a plurality of layers of organic silicon/epoxy films and a plurality of layers of fiber cloth according to claim 6, arranging the layers of organic silicon/epoxy films and the layers of fiber cloth at intervals in a lamination mode to obtain a prefabricated body, wherein the upper surface and the lower surface of the prefabricated body are both the organic silicon/epoxy films, preparing the prefabricated body into a composite board through hot pressing, and then bending the laminated board.
8. The flexible laminate of claim 7, wherein: the fiber cloth comprises one or more of quartz fiber cloth, hollow quartz fiber cloth, high silica fiber cloth, glass fiber cloth, aramid fiber cloth, PBO fiber cloth and super-molecular weight polyethylene fiber cloth.
9. The flexible laminate of claim 7, wherein: the hot pressing temperature is 150-180 ℃, the hot pressing pressure is 1-5MPa, and the hot pressing time is 0.5-2 hours.
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