CN114987024A - Composite wrench cover with textures and production process thereof - Google Patents

Composite wrench cover with textures and production process thereof Download PDF

Info

Publication number
CN114987024A
CN114987024A CN202210536606.1A CN202210536606A CN114987024A CN 114987024 A CN114987024 A CN 114987024A CN 202210536606 A CN202210536606 A CN 202210536606A CN 114987024 A CN114987024 A CN 114987024A
Authority
CN
China
Prior art keywords
fiber cloth
silicon dioxide
glass fiber
silane coupling
coupling agent
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.)
Granted
Application number
CN202210536606.1A
Other languages
Chinese (zh)
Other versions
CN114987024B (en
Inventor
张宗权
何辉春
王碧武
陈建
陈欢
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Zongsheng New Materials Co.,Ltd.
Original Assignee
Huizhou Zongsheng Electronic Material Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Huizhou Zongsheng Electronic Material Co ltd filed Critical Huizhou Zongsheng Electronic Material Co ltd
Priority to CN202210536606.1A priority Critical patent/CN114987024B/en
Publication of CN114987024A publication Critical patent/CN114987024A/en
Application granted granted Critical
Publication of CN114987024B publication Critical patent/CN114987024B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Reinforced Plastic Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a composite wrench cover with textures and a production process thereof, the scheme is that glue solution is coated on two sides of continuous glass fiber cloth and then the glue solution is cured to form prepreg, then a plurality of prepregs are stacked from top to bottom in sequence, a texture film can be placed on the uppermost layer during actual processing, the texture film comprises a PET bottom layer (PET release paper) and a UV (ultraviolet) glue layer containing texture patterns, the UV glue layer is contacted with the prepreg on the uppermost layer during placement, hot pressing and compounding are carried out to form a mobile phone cover plate with the texture film, the PET bottom layer (PET release paper) above the mobile phone cover plate is torn off, and the UV glue layer containing the texture patterns is transferred to the upper surface of the mobile phone cover plate, so that the texture patterns are formed on the surface of the mobile phone cover plate, the texture patterns are not easy to fall off, and the practicability is more excellent. The prepared composite mobile phone cover plate has excellent strength and mechanical property, excellent surface waterproof and moistureproof performance, excellent high temperature resistance and high practicability.

Description

Composite wrench cover with textures and production process thereof
Technical Field
The invention relates to the technical field of mobile phone cover plates, in particular to a composite board mobile phone cover with textures and a production process thereof.
Background
The glass fiber is an inorganic non-metallic material with excellent performance, has various varieties, has the advantages of good insulativity, strong heat resistance, good corrosion resistance and high mechanical strength, but has the defects of brittleness and poor wear resistance. Glass fibers are commonly used as reinforcing materials in composite materials, and are widely used in various fields. Nowadays, with the rapid development of electronic products, the performance requirements of consumers on mobile phone covers are higher and higher, and the requirements on surface patterns and decoration aesthetics are also relatively higher, and on this basis, improving the strength and high temperature resistance of mobile phone covers is the main content of research and development.
Therefore, the application discloses a composite wrench cover with textures and a production process thereof based on the above situation so as to prepare a high-strength cover plate material.
Disclosure of Invention
The invention aims to provide a composite wrench cover with textures and a production process thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a production process of a composite wrench cover with textures comprises the following steps:
(1) mixing graphene oxide and deionized water, stirring for 20-30 min, and ultrasonically dispersing for 1-1.5 h to obtain a graphene dispersion liquid;
mixing a silane coupling agent A and ethanol to obtain a mixed solution; taking silicon dioxide and deionized water, ultrasonically stirring for 20-30 min, adding the mixed solution at 50-60 ℃, reacting for 1-1.5 h under heat preservation, then heating to 70-80 ℃, and carrying out heat preservation treatment for 2-2.5 h to obtain a silicon dioxide dispersion solution; the silane coupling agent A is a mixture of KH-550 and KH-560;
(2) soaking the continuous glass fiber cloth into the graphene dispersion liquid for 10-20 min, taking out and vacuum-drying; soaking in a silicon dioxide dispersion liquid, standing for 15-20 min, adjusting the pH value of the silicon dioxide dispersion liquid to 8-9, heating to 65-75 ℃, keeping the temperature for reaction for 2-3 h, adding gamma-mercaptopropyl trimethoxysilane, continuing stirring for 20-30 min, taking out, and drying in vacuum to obtain graphene oxide-silicon dioxide loaded fiber cloth;
mixing an epoxy monomer containing allyl with toluene to obtain an epoxy monomer solution; soaking the fiber cloth loaded with graphene oxide-silicon dioxide into an epoxy monomer solution, stirring and reacting for 30-40 min under a nitrogen environment at the reaction temperature of 85-90 ℃, adding azobisisobutyronitrile, continuing to react for 10-12 h, taking out after reaction, washing and drying to obtain modified glass fiber cloth;
(3) mixing epoxy resin and an epoxy monomer containing allyl, adding a curing agent, and uniformly mixing to obtain a glue solution; coating glue solution on two sides of modified glass fiber cloth, and curing to form a prepreg;
and taking a plurality of layers of prepreg to stack from top to bottom, placing a texture film on the upper surface, wherein the texture film comprises a PET (polyethylene terephthalate) bottom layer and a UV (ultraviolet) adhesive layer with texture patterns, contacting the UV adhesive layer with the prepreg, performing hot-pressing compounding, and removing the PET bottom layer to obtain the textured mobile phone cover.
In a preferred embodiment, the preparation step of the allyl group-containing epoxy monomer comprises:
s1: dissolving a diphenol monomer in absolute ethyl alcohol, adding anhydrous potassium carbonate, heating to 80-85 ℃, stirring for reaction for 1-1.5 hours, slowly dropwise adding allyl bromide during reaction, continuing to react for 6-8 hours, collecting a product after the reaction, sequentially washing with absolute ethyl alcohol and deionized water, drying in vacuum, heating to 170-180 ℃ under a nitrogen atmosphere, carrying out heat preservation treatment for 20-30 min, continuing to heat to 210-215 ℃, and carrying out heat preservation reaction for 1.5-2 hours to obtain a monomer containing allyl; the diphenol monomer comprises 3-fluorobiphenyl-4, 4 '-diphenol, 4' -amino-4-diphenol and diphenol;
s2: taking a monomer containing allyl, epoxy chloropropane, benzyltriethylammonium chloride and dioxane, mixing and stirring for 20-30 min, heating to 90-95 ℃, stirring and reacting for 4-5 h, collecting a product after the reaction, mixing the product with toluene, dripping a sodium hydroxide solution at 85-90 ℃, continuing to react for 4-5 h, washing with deionized water after the reaction, and drying in vacuum to obtain the epoxy monomer containing allyl.
In a more preferable embodiment, in step S1, the molar ratio of the 3-fluorobiphenyl-4, 4 '-diol, the 4' -amino-4-biphenol and the biphenol is 1: 1: 1; the molar ratio of the diphenol monomer to the anhydrous potassium carbonate to the allyl bromide is 1: (2.5-3): (4-5).
In an optimized scheme, in step S2, the molar ratio of the allyl-containing monomer to epichlorohydrin to benzyltriethylammonium chloride is 1: 4: 0.5.
in the optimized scheme, in the step (1), the molar ratio of KH-550 to KH-560 is 3: 1; the mass ratio of the silicon dioxide to the silane coupling agent A is 10: 1, the molar ratio of the KH-550 to the gamma-mercaptopropyltrimethoxysilane is 1: 3.
according to an optimized scheme, in the step (2), the continuous glass fiber cloth is pretreated, and the method specifically comprises the following steps: taking a silane coupling agent B, absolute ethyl alcohol and deionized water, and carrying out ultrasonic dispersion for 20-30 min to obtain a silane coupling agent solution; and soaking the continuous glass fiber cloth into a silane coupling agent solution for 20-30 min, taking out, and performing vacuum drying to obtain the pretreated continuous glass fiber cloth.
In an optimized scheme, the silane coupling agent B is KH-843.
According to an optimized scheme, the mass ratio of the epoxy resin, the epoxy monomer containing allyl and the curing agent is 5: 1: 1.5; the curing agent is polyamide 650.
According to an optimized scheme, the mobile phone cover is prepared by the production process of the composite board mobile phone cover with the texture.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a production process of a composite wrench cover with textures, which comprises the steps of coating glue solution on two sides of continuous glass fiber cloth, curing to form prepreg, sequentially stacking a plurality of prepregs from top to bottom, placing a texture film on the uppermost layer during actual processing, contacting the UV adhesive layer with the prepreg on the uppermost layer during placement, performing hot-pressing compounding to form a mobile phone cover plate with the texture film, tearing off the PET adhesive layer (PET release paper) above the mobile phone cover plate, and transferring the UV adhesive layer containing the texture pattern to the upper surface of the mobile phone cover plate, so that the texture pattern is formed on the surface of the mobile phone cover plate, is not easy to fall off, and has more excellent practicability. The texture pattern is a cobblestone pattern or a diamond pattern.
According to the scheme, continuous glass fibers are arranged in graphene dispersion liquid, graphene is deposited and soaked on the surface of the continuous glass fiber cloth, then the continuous glass fiber cloth is placed in silicon dioxide dispersion liquid treated by a silane coupling agent A to adsorb and deposit silicon dioxide, the glass fiber cloth with the surface loaded with graphene oxide and silicon dioxide is obtained, graphene oxide and silicon dioxide are sequentially deposited on the surface of the glass fiber cloth outwards, the graphene oxide and the silicon dioxide can serve as reinforcing frameworks, and the strength and the mechanical property of the mobile phone cover plate can be greatly improved after glue liquid is solidified.
In this step, the following conditions need to be defined:
(1) the silane coupling agent A introduced into the silicon dioxide dispersion liquid is a mixture of KH-550 and KH-560, and the molar ratio of KH-550 to KH-560 is 3: 1; the purpose of this defining parameter is to: the surface of the graphene oxide is negatively charged, and amino groups are introduced to the surface of the silicon dioxide, so that the silicon dioxide and the graphene oxide can be assembled in an electrostatic manner, and the silicon dioxide is deposited and impregnated on the surface of the graphene oxide to form a reinforced structure; on the other hand, the introduction of the epoxy group is to improve the compatibility between the subsequent epoxy resin glue solution, improve the adhesion and wettability of the glue solution on the surface of the continuous glass fiber cloth, and improve the crosslinking density of the glue solution, so that the strength and the mechanical property of the mobile phone cover plate are improved.
(2) Soaking the continuous glass fiber cloth into the silicon dioxide dispersion liquid, and adjusting the pH to 8-9 for reaction; the reasons for the adjustment of this parameter are: at the moment, amino groups and epoxy groups exist on the surface of the silicon dioxide, and in an alkaline environment, the amino groups on the surface of the silicon dioxide open rings to realize bridging among silicon dioxide particles, so that the deposition effect of the silicon dioxide can be improved, the reinforcing effect of the silicon dioxide is improved, and the strength of a finished cover plate is further improved.
(3) After the pH value of the system is adjusted, adding gamma-mercaptopropyl trimethoxy silane for reaction; the purpose of this step is: the method is characterized in that a sulfydryl group is introduced to the surface of a glass fiber loaded with graphene oxide and silicon dioxide, and the method mainly comprises the following steps: in the conventional step, gamma-mercaptopropyl trimethoxy silane can be completely added into a silane coupling agent A or a silane coupling agent B to directly pretreat silicon dioxide or continuous glass fiber cloth so as to introduce mercapto groups, but in the scheme, the negative charges of graphene oxide and the electrostatic interaction of amino silicon dioxide are utilized, so that the electrostatic assembly effect is prevented from being influenced, and the adding sequence of the mercapto silane coupling agent is adjusted to be after deposition and adsorption so as to reduce the influence caused by the mercapto groups.
On the basis of the scheme, the epoxy monomer containing allyl is grafted on the surface of the glass fiber cloth loaded with graphene oxide-silicon dioxide, and the epoxy monomer is grafted to the surface of the glass fiber cloth through a mercapto-alkene click reaction, so that the adhesiveness of the surface of the continuous glass fiber cloth and an epoxy resin glue solution is improved, the epoxy monomer contained on the surface of the continuous glass fiber cloth can participate in curing of the resin glue solution, the curing and coating effects of the resin glue solution are effectively improved, and the strength of the prepreg is greatly improved.
Meanwhile, the epoxy monomer containing allyl is prepared by taking a diphenol monomer as a raw material, and the scheme limits that the diphenol monomer comprises 3-fluorobiphenyl-4, 4 '-diphenol, 4' -amino-4-diphenol and diphenol, and the molar ratio is 1: 1: 1', the epoxy monomer contains fluorine element and biphenyl unit, the introduction of the biphenyl unit can improve the high temperature resistance of the epoxy resin, the introduction of the fluorine element can effectively improve the waterproof and moistureproof capacity of the mobile phone cover plate, and meanwhile, the epoxy monomer containing allyl is introduced into an epoxy resin curing system, so that the crosslinking density of glue solution can be improved, and the strength of the mobile phone cover plate is influenced excellently.
According to the scheme, the continuous glass fiber cloth is pretreated, the silane coupling agent KH-843 is adopted to pretreat the continuous glass fiber, the KH-843 is a bisaminosilane coupling agent, and after the continuous glass fiber cloth is pretreated, the deposition of graphene oxide on the surface of the continuous glass fiber cloth can be effectively improved; meanwhile, the introduction of the amino group can further improve the adhesion of the continuous glass fiber cloth and the subsequent epoxy glue solution, and the mechanical property of the cured product is improved.
The scheme discloses a production process of a composite mobile phone cover with textures, the process is reasonable in design and simple in operation, the prepared composite mobile phone cover plate has excellent strength and mechanical property, the surface of the composite mobile phone cover plate is excellent in waterproof and moisture-proof performance, and the composite mobile phone cover plate is excellent in high-temperature resistance and has high practicability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In embodiments 1 to 4 of this embodiment, the specific preparation steps of the allyl group-containing epoxy monomer are as follows:
s1: dissolving a diphenol monomer in absolute ethyl alcohol, adding anhydrous potassium carbonate, heating to 80 ℃, stirring for reaction for 1.5 hours, slowly dropwise adding allyl bromide during reaction, continuing to react for 7 hours, collecting a product after the reaction, sequentially washing with the absolute ethyl alcohol and deionized water, drying in vacuum, heating to 170 ℃ under a nitrogen atmosphere, carrying out heat preservation treatment for 30min, continuing to heat to 210 ℃, and carrying out heat preservation reaction for 2 hours to obtain a monomer containing allyl; the diphenol monomer comprises 3-fluorobiphenyl-4, 4 '-diphenol, 4' -amino-4-diphenol and diphenol; the molar ratio of the 3-fluorobiphenyl-4, 4 '-diphenol to the 4' -amino-4-diphenol to the diphenol is 1: 1: 1; the molar ratio of the diphenol monomer to the anhydrous potassium carbonate to the allyl bromide is 1: 2.5: 4.
s2: taking a monomer containing allyl, epichlorohydrin, benzyltriethylammonium chloride and dioxane, mixing and stirring for 30min, heating to 90 ℃, stirring and reacting for 5h, collecting a product after the reaction, mixing the product with toluene, dripping sodium hydroxide solution at 85 ℃, continuing the reaction for 5h, washing with deionized water after the reaction, and drying in vacuum to obtain the epoxy monomer containing allyl. The molar ratio of the allyl-containing monomer to the epichlorohydrin to the benzyltriethylammonium chloride is 1: 4: 0.5; the molar ratio of the allyl-containing monomer to sodium hydroxide is 1: 2.
the scheme is mainly characterized in that the prepreg is prepared, so that in order to avoid the influence of UV (ultraviolet) glue, a texture film is not required to be pasted for convenient detection in actual preparation; the model of the scheme glass fiber cloth is 2116.
Example 1:
a production process of a composite wrench cover with textures comprises the following steps:
(1) mixing graphene oxide and deionized water, stirring for 20min, and performing ultrasonic dispersion for 1h to obtain graphene dispersion liquid with the concentration of 4 g/L;
mixing a silane coupling agent A with ethanol with equal mass to obtain a mixed solution; the silane coupling agent A is a mixture of KH-550 and KH-560, wherein the molar ratio of KH-550 to KH-560 is 3: 1.
taking silicon dioxide and deionized water, ultrasonically stirring for 20min, adding the mixed solution at 50 ℃, carrying out heat preservation reaction for 1.5h, then heating to 70 ℃, and carrying out heat preservation treatment for 2.5h to obtain a silicon dioxide dispersion solution; the mass ratio of the silicon dioxide to the deionized water is 1: 50; the mass ratio of the silicon dioxide to the silane coupling agent A is 10: 1.
(2) soaking the continuous glass fiber cloth in the graphene dispersion liquid for 10min, taking out and vacuum-drying; drying, soaking in a silicon dioxide dispersion liquid, standing for 15min, adjusting the pH value of the silicon dioxide dispersion liquid to 8, heating to 65 ℃, keeping the temperature for reaction for 3h, adding gamma-mercaptopropyl trimethoxy silane, continuing stirring for 20min, taking out, and drying in vacuum to obtain graphene oxide-silicon dioxide loaded fiber cloth; the bath ratio is 1: 10. the molar ratio of the KH-550 to the gamma-mercaptopropyltrimethoxysilane is 1: 3.
mixing an epoxy monomer containing allyl with toluene to obtain an epoxy monomer solution; the concentration of the epoxy monomer solution is 4 g/L; soaking the fiber cloth loaded with graphene oxide-silicon dioxide into an epoxy monomer solution, stirring and reacting for 30min under a nitrogen environment, wherein the reaction temperature is 90 ℃, adding azobisisobutyronitrile, continuing to react for 10h, taking out after the reaction, washing and drying to obtain modified glass fiber cloth; the using amount of the azodiisobutyronitrile is 1 wt% of the epoxy monomer; the mass ratio of the graphene oxide-silicon dioxide loaded fiber cloth to the epoxy monomer is 1: 8.
(3) mixing epoxy resin and an epoxy monomer containing allyl, adding a curing agent, and uniformly mixing to obtain a glue solution; coating glue solution on two sides of modified glass fiber cloth, and curing to form a prepreg; the coating weight was 250g/m 2 。
The mass ratio of the epoxy resin to the allyl-containing epoxy monomer to the curing agent is 5: 1: 1.5; the curing agent is polyamide 650.
And (5) stacking the four layers of prepregs from top to bottom, and performing hot-pressing compounding to obtain a finished product.
Example 2:
a production process of a composite wrench cover with textures comprises the following steps:
(1) mixing graphene oxide and deionized water, stirring for 25min, and performing ultrasonic dispersion for 1.5h to obtain a graphene dispersion liquid with the concentration of 4 g/L;
mixing a silane coupling agent A with ethanol with equal mass to obtain a mixed solution; the silane coupling agent A is a mixture of KH-550 and KH-560, wherein the molar ratio of KH-550 to KH-560 is 3: 1.
taking silicon dioxide and deionized water, ultrasonically stirring for 25min, adding the mixed solution at 55 ℃, carrying out heat preservation reaction for 1.5h, then heating to 75 ℃, and carrying out heat preservation treatment for 2.5h to obtain a silicon dioxide dispersion solution; the mass ratio of the silicon dioxide to the deionized water is 1: 50; the mass ratio of the silicon dioxide to the silane coupling agent A is 10: 1.
(2) soaking the continuous glass fiber cloth into the graphene dispersion liquid for 15min, taking out and vacuum-drying; drying, soaking in a silicon dioxide dispersion liquid, standing for 18min, adjusting the pH value of the silicon dioxide dispersion liquid to 9, heating to 70 ℃, keeping the temperature for reaction for 2.5h, adding gamma-mercaptopropyl trimethoxy silane, continuing stirring for 25min, taking out, and drying in vacuum to obtain graphene oxide-silicon dioxide loaded fiber cloth; the bath ratio is 1: 10. the molar ratio of the KH-550 to the gamma-mercaptopropyltrimethoxysilane is 1: 3.
mixing an epoxy monomer containing allyl with toluene to obtain an epoxy monomer solution; the concentration of the epoxy monomer solution is 4 g/L; soaking the fiber cloth loaded with graphene oxide-silicon dioxide into an epoxy monomer solution, stirring and reacting for 35min under a nitrogen environment, adding azobisisobutyronitrile at the reaction temperature of 90 ℃, continuing to react for 11h, taking out after reaction, washing and drying to obtain modified glass fiber cloth; the using amount of the azodiisobutyronitrile is 1 wt% of the epoxy monomer; the mass ratio of the graphene oxide-silicon dioxide loaded fiber cloth to the epoxy monomer is 1: 8.
(3) mixing epoxy resin and an epoxy monomer containing allyl, adding a curing agent, and uniformly mixing to obtain a glue solution; coating glue solution on two sides of modified glass fiber cloth, and curing to form a prepreg; the coating amount was 250g/m 2 。
The mass ratio of the epoxy resin to the epoxy monomer containing allyl and the curing agent is 5: 1: 1.5; the curing agent is polyamide 650.
And (5) stacking the four layers of prepregs from top to bottom, and performing hot-pressing compounding to obtain a finished product.
Example 3:
a production process of a composite wrench cover with textures comprises the following steps:
(1) mixing graphene oxide and deionized water, stirring for 30min, and performing ultrasonic dispersion for 1.5h to obtain a graphene dispersion liquid with the concentration of 4 g/L;
mixing a silane coupling agent A with ethanol with equal mass to obtain a mixed solution; the silane coupling agent A is a mixture of KH-550 and KH-560, and the molar ratio of KH-550 to KH-560 is 3: 1.
taking silicon dioxide and deionized water, ultrasonically stirring for 30min, adding the mixed solution at 60 ℃, carrying out heat preservation reaction for 1h, then heating to 80 ℃, and carrying out heat preservation treatment for 2h to obtain a silicon dioxide dispersion solution; the mass ratio of the silicon dioxide to the deionized water is 1: 50; the mass ratio of the silicon dioxide to the silane coupling agent A is 10: 1.
(2) soaking the continuous glass fiber cloth in the graphene dispersion liquid for 20min, taking out and vacuum-drying; drying, soaking in a silicon dioxide dispersion liquid, standing for 20min, adjusting the pH value of the silicon dioxide dispersion liquid to 9, heating to 75 ℃, keeping the temperature for reaction for 2h, adding gamma-mercaptopropyl trimethoxy silane, continuing stirring for 30min, taking out, and drying in vacuum to obtain graphene oxide-silicon dioxide loaded fiber cloth; the bath ratio is 1: 10. the molar ratio of the KH-550 to the gamma-mercaptopropyltrimethoxysilane is 1: 3.
mixing an epoxy monomer containing allyl with toluene to obtain an epoxy monomer solution; the concentration of the epoxy monomer solution is 4 g/L; soaking the fiber cloth loaded with graphene oxide-silicon dioxide into an epoxy monomer solution, stirring and reacting for 40min under a nitrogen environment, keeping the reaction temperature at 85 ℃, adding azobisisobutyronitrile, continuing to react for 12h, taking out after the reaction, washing and drying to obtain modified glass fiber cloth; the using amount of the azodiisobutyronitrile is 1 wt% of the epoxy monomer; the mass ratio of the graphene oxide-silicon dioxide loaded fiber cloth to the epoxy monomer is 1: 8.
(3) mixing epoxy resin and an epoxy monomer containing allyl, adding a curing agent, and uniformly mixing to obtain a glue solution; coating glue solution on two sides of modified glass fiber cloth, and curing to form a prepreg; the coating weight was 250g/m 2 。
The mass ratio of the epoxy resin to the allyl-containing epoxy monomer to the curing agent is 5: 1: 1.5; the curing agent is polyamide 650.
And (5) stacking the four layers of prepregs from top to bottom, and performing hot-pressing compounding to obtain a finished product.
Example 4: the continuous glass fiber cloth was pretreated on the basis of example 2, and the rest of the process was unchanged.
A production process of a composite wrench cover with textures comprises the following steps:
(1) mixing graphene oxide and deionized water, stirring for 25min, and performing ultrasonic dispersion for 1.5h to obtain a graphene dispersion liquid with the concentration of 4 g/L;
mixing a silane coupling agent A with ethanol with equal mass to obtain a mixed solution; the silane coupling agent A is a mixture of KH-550 and KH-560, and the molar ratio of KH-550 to KH-560 is 3: 1.
taking silicon dioxide and deionized water, ultrasonically stirring for 25min, adding the mixed solution at 55 ℃, carrying out heat preservation reaction for 1.5h, then heating to 75 ℃, and carrying out heat preservation treatment for 2.5h to obtain a silicon dioxide dispersion solution; the mass ratio of the silicon dioxide to the deionized water is 1: 50; the mass ratio of the silicon dioxide to the silane coupling agent A is 10: 1.
(2) taking a silane coupling agent B, absolute ethyl alcohol and deionized water, and carrying out ultrasonic dispersion for 25min to obtain a silane coupling agent solution; and soaking the continuous glass fiber cloth into a silane coupling agent solution for 25min, taking out, and performing vacuum drying to obtain the pretreated continuous glass fiber cloth. The silane coupling agent B is KH-843, and the mass ratio of the silane coupling agent B to the absolute ethyl alcohol to the deionized water is 5: 12: 2; the bath ratio is 1: 10.
soaking the pretreated continuous glass fiber cloth into the graphene dispersion liquid for 15min, taking out and vacuum-drying; drying, soaking in a silicon dioxide dispersion liquid, standing for 18min, adjusting the pH value of the silicon dioxide dispersion liquid to 9, heating to 70 ℃, keeping the temperature for reaction for 2.5h, adding gamma-mercaptopropyl trimethoxy silane, continuing stirring for 25min, taking out, and drying in vacuum to obtain graphene oxide-silicon dioxide loaded fiber cloth; the bath ratio is 1: 10. the molar ratio of the KH-550 to the gamma-mercaptopropyltrimethoxysilane is 1: 3.
mixing an epoxy monomer containing allyl with toluene to obtain an epoxy monomer solution; the concentration of the epoxy monomer solution is 4 g/L; soaking the fiber cloth loaded with graphene oxide-silicon dioxide into an epoxy monomer solution, stirring and reacting for 35min under a nitrogen environment, adding azobisisobutyronitrile at the reaction temperature of 90 ℃, continuing to react for 11h, taking out after reaction, washing and drying to obtain modified glass fiber cloth; the using amount of the azodiisobutyronitrile is 1 wt% of the epoxy monomer; the mass ratio of the graphene oxide-silicon dioxide loaded fiber cloth to the epoxy monomer is 1: 8.
(3) mixing epoxy resin and an epoxy monomer containing allyl, adding a curing agent, and uniformly mixing to obtain a glue solution; coating glue solution on two sides of modified glass fiber cloth, and curing to form a prepreg; the coating weight was 250g/m 2 。
The mass ratio of the epoxy resin to the allyl-containing epoxy monomer to the curing agent is 5: 1: 1.5; the curing agent is polyamide 650.
And (5) stacking the four layers of prepregs from top to bottom, and performing hot-pressing compounding to obtain a finished product.
Comparative example 1: a control was carried out on the basis of example 4, in comparative example 1, the allyl group-containing epoxy monomer was prepared without adding 4' -amino-4-biphenol.
The specific parameters are as follows: the diphenol monomer comprises 3-fluorobiphenyl-4, 4' -diphenol and diphenol; the molar ratio of the 3-fluorobiphenyl-4, 4' -diphenol to the diphenol is 1: 1; the molar ratio of the diphenol monomer to the anhydrous potassium carbonate to the allyl bromide is 1: 2.5: 3.
comparative example 2: a control was made on the basis of example 4, comparative example 2, in which the allyl-containing epoxy monomer was prepared without the addition of 3-fluorobiphenyl-4, 4' -diol.
The specific parameters are as follows: the diphenol monomer comprises 4' -amino-4-diphenol and diphenol; the molar ratio of the 4' -amino-4-diphenol to the diphenol is 1: 1; the molar ratio of the diphenol monomer to the anhydrous potassium carbonate to the allyl bromide is 1: 2.5: 3.
comparative example 3: a comparison was made on the basis of example 4, and in comparative example 3, the molar ratio of KH-550 to KH-560 in the silane coupling agent A was adjusted to 2: 1.
comparative example 4: a comparison was made on the basis of example 4, and in comparative example 4, the molar ratio of KH-550 to KH-560 in the silane coupling agent A was adjusted to 2: 1, and defining the molar ratio of KH-550 to gamma-mercaptopropyltrimethoxysilane to be 1: 1.
comparative example 5: a comparison was made on the basis of example 4, and in comparative example 5, in which the order of addition of the silane coupling agent was not limited, KH-550, KH-560, and gamma-mercaptopropyltrimethoxysilane were added together.
A production process of a composite wrench cover with textures comprises the following steps:
(1) mixing graphene oxide and deionized water, stirring for 25min, and performing ultrasonic dispersion for 1.5h to obtain a graphene dispersion liquid with the concentration of 4 g/L;
mixing a silane coupling agent A with ethanol with equal mass to obtain a mixed solution; the silane coupling agent A is a mixture of KH-550, KH-560 and gamma-mercaptopropyltrimethoxysilane, wherein the molar ratio of the KH-550 to the KH-560 to the gamma-mercaptopropyltrimethoxysilane is 3: 1: 9.
taking silicon dioxide and deionized water, ultrasonically stirring for 25min, adding the mixed solution at 55 ℃, carrying out heat preservation reaction for 1.5h, then heating to 75 ℃, and carrying out heat preservation treatment for 2.5h to obtain a silicon dioxide dispersion solution; the mass ratio of the silicon dioxide to the deionized water is 1: 50; the mass ratio of the silicon dioxide to the silane coupling agent A is 10: 1.
(2) taking a silane coupling agent B, absolute ethyl alcohol and deionized water, and carrying out ultrasonic dispersion for 25min to obtain a silane coupling agent solution; and soaking the continuous glass fiber cloth into a silane coupling agent solution for 25min, taking out, and performing vacuum drying to obtain the pretreated continuous glass fiber cloth. The silane coupling agent B is KH-843, and the mass ratio of the silane coupling agent B to the absolute ethyl alcohol to the deionized water is 5: 12: 2; the bath ratio is 1: 10.
soaking the pretreated continuous glass fiber cloth into the graphene dispersion liquid for 15min, taking out and vacuum-drying; drying, soaking in a silicon dioxide dispersion liquid, standing for 18min, adjusting the pH value of the silicon dioxide dispersion liquid to 9, heating to 70 ℃, carrying out heat preservation reaction for 2.5h, taking out, and carrying out vacuum drying to obtain graphene oxide-silicon dioxide loaded fiber cloth; the bath ratio is 1: 10.
mixing an epoxy monomer containing allyl with toluene to obtain an epoxy monomer solution; the concentration of the epoxy monomer solution is 4 g/L; soaking the fiber cloth loaded with graphene oxide-silicon dioxide into an epoxy monomer solution, stirring and reacting for 35min under a nitrogen environment, adding azobisisobutyronitrile at the reaction temperature of 90 ℃, continuing to react for 11h, taking out after reaction, washing and drying to obtain modified glass fiber cloth; the using amount of the azodiisobutyronitrile is 1 wt% of the epoxy monomer; the mass ratio of the graphene oxide-silicon dioxide loaded fiber cloth to the epoxy monomer is 1: 8.
(3) mixing epoxy resin and an epoxy monomer containing allyl, adding a curing agent, and uniformly mixing to obtain a glue solution; coating glue solution on two sides of modified glass fiber cloth, and curing to form a prepreg; the coating weight was 250g/m 2 。
The mass ratio of the epoxy resin to the allyl-containing epoxy monomer to the curing agent is 5: 1: 1.5; the curing agent is polyamide 650.
And (5) stacking the four layers of prepregs from top to bottom, and performing hot-pressing compounding to obtain a finished product.
Comparative example 6: a comparison was made on the basis of example 4, and in comparative example 6, the order of addition of the silane coupling agent was not limited, and KH-550, KH-560, and gamma-mercaptopropyltrimethoxysilane were added together.
A production process of a composite wrench cover with textures comprises the following steps:
(1) mixing graphene oxide and deionized water, stirring for 25min, and performing ultrasonic dispersion for 1.5h to obtain a graphene dispersion liquid with the concentration of 4 g/L;
mixing a silane coupling agent A with ethanol with equal mass to obtain a mixed solution; the silane coupling agent A is a mixture of KH-550, KH-560 and gamma-mercaptopropyltrimethoxysilane, wherein the molar ratio of the KH-550 to the KH-560 to the gamma-mercaptopropyltrimethoxysilane is 3: 1: 2.
taking silicon dioxide and deionized water, ultrasonically stirring for 25min, adding the mixed solution at 55 ℃, carrying out heat preservation reaction for 1.5h, then heating to 75 ℃, and carrying out heat preservation treatment for 2.5h to obtain a silicon dioxide dispersion solution; the mass ratio of the silicon dioxide to the deionized water is 1: 50; the mass ratio of the silicon dioxide to the silane coupling agent A is 10: 1.
(2) taking a silane coupling agent B, absolute ethyl alcohol and deionized water, and carrying out ultrasonic dispersion for 25min to obtain a silane coupling agent solution; and soaking the continuous glass fiber cloth into a silane coupling agent solution for 25min, taking out, and performing vacuum drying to obtain the pretreated continuous glass fiber cloth. The silane coupling agent B is KH-843, and the mass ratio of the silane coupling agent B to the absolute ethyl alcohol to the deionized water is 5: 12: 2; the bath ratio is 1: 10.
soaking the pretreated continuous glass fiber cloth into the graphene dispersion liquid for 15min, taking out and vacuum-drying; drying, soaking in a silicon dioxide dispersion liquid, standing for 18min, adjusting the pH value of the silicon dioxide dispersion liquid to 9, heating to 70 ℃, carrying out heat preservation reaction for 2.5h, taking out, and carrying out vacuum drying to obtain graphene oxide-silicon dioxide loaded fiber cloth; the bath ratio is 1: 10.
mixing an epoxy monomer containing allyl with toluene to obtain an epoxy monomer solution; the concentration of the epoxy monomer solution is 4 g/L; soaking the fiber cloth loaded with graphene oxide-silicon dioxide into an epoxy monomer solution, stirring and reacting for 35min under a nitrogen environment, adding azobisisobutyronitrile at the reaction temperature of 90 ℃, continuing to react for 11h, taking out after reaction, washing and drying to obtain modified glass fiber cloth; the dosage of the azodiisobutyronitrile is 1 wt% of the epoxy monomer; the mass ratio of the graphene oxide-silicon dioxide loaded fiber cloth to the epoxy monomer is 1: 8.
(3) taking epoxy resin and ring containing allylMixing oxygen monomers, adding a curing agent, and uniformly mixing to obtain a glue solution; coating glue solution on two sides of modified glass fiber cloth, and curing to form a prepreg; the coating weight was 250g/m 2 。
The mass ratio of the epoxy resin to the allyl-containing epoxy monomer to the curing agent is 5: 1: 1.5; the curing agent is polyamide 650.
And (4) stacking four layers of prepregs from top to bottom, and performing hot-pressing compounding to obtain a finished product.
Comparative example 7: a control was made on the basis of example 4, comparative example 7 without adding an allyl-containing epoxy monomer to the gum solution.
A production process of a composite wrench cover with textures comprises the following steps:
(1) mixing graphene oxide and deionized water, stirring for 25min, and performing ultrasonic dispersion for 1.5h to obtain a graphene dispersion liquid with the concentration of 4 g/L;
mixing a silane coupling agent A with ethanol with equal mass to obtain a mixed solution; the silane coupling agent A is a mixture of KH-550 and KH-560, and the molar ratio of KH-550 to KH-560 is 3: 1.
taking silicon dioxide and deionized water, ultrasonically stirring for 25min, adding the mixed solution at 55 ℃, carrying out heat preservation reaction for 1.5h, then heating to 75 ℃, and carrying out heat preservation treatment for 2.5h to obtain a silicon dioxide dispersion solution; the mass ratio of the silicon dioxide to the deionized water is 1: 50; the mass ratio of the silicon dioxide to the silane coupling agent A is 10: 1.
(2) taking a silane coupling agent B, absolute ethyl alcohol and deionized water, and carrying out ultrasonic dispersion for 25min to obtain a silane coupling agent solution; and soaking the continuous glass fiber cloth into a silane coupling agent solution for 25min, taking out, and performing vacuum drying to obtain the pretreated continuous glass fiber cloth. The silane coupling agent B is KH-843, and the mass ratio of the silane coupling agent B to the absolute ethyl alcohol to the deionized water is 5: 12: 2; the bath ratio is 1: 10.
soaking the pretreated continuous glass fiber cloth into the graphene dispersion liquid for 15min, taking out and vacuum-drying; drying, soaking in a silicon dioxide dispersion liquid, standing for 18min, adjusting the pH value of the silicon dioxide dispersion liquid to 9, heating to 70 ℃, keeping the temperature for reaction for 2.5h, adding gamma-mercaptopropyl trimethoxy silane, continuing stirring for 25min, taking out, and drying in vacuum to obtain graphene oxide-silicon dioxide loaded fiber cloth; the bath ratio is 1: 10. the molar ratio of the KH-550 to the gamma-mercaptopropyltrimethoxysilane is 1: 3.
mixing an epoxy monomer containing allyl with toluene to obtain an epoxy monomer solution; the concentration of the epoxy monomer solution is 4 g/L; soaking the fiber cloth loaded with graphene oxide-silicon dioxide into an epoxy monomer solution, stirring and reacting for 35min under a nitrogen environment, wherein the reaction temperature is 90 ℃, adding azobisisobutyronitrile, continuing to react for 11h, taking out after the reaction, washing and drying to obtain modified glass fiber cloth; the dosage of the azodiisobutyronitrile is 1 wt% of the epoxy monomer; the mass ratio of the graphene oxide-silicon dioxide loaded fiber cloth to the epoxy monomer is 1: 8.
(3) taking epoxy resin, adding a curing agent, and uniformly mixing to obtain a glue solution; coating glue solution on two sides of modified glass fiber cloth, and curing to form a prepreg; the coating weight was 250g/m 2 . The mass ratio of the epoxy resin to the curing agent is 4: 1; the curing agent is polyamide 650.
And (4) stacking four layers of prepregs from top to bottom, and performing hot-pressing compounding to obtain a finished product.
Comparative example 8: a control was made on the basis of example 4, comparative example 8 without silica being introduced.
A production process of a composite wrench cover with textures comprises the following steps:
(1) mixing graphene oxide and deionized water, stirring for 25min, and performing ultrasonic dispersion for 1.5h to obtain a graphene dispersion liquid with the concentration of 4 g/L;
(2) taking a silane coupling agent B, absolute ethyl alcohol and deionized water, and carrying out ultrasonic dispersion for 25min to obtain a silane coupling agent solution; and soaking the continuous glass fiber cloth into a silane coupling agent solution for 25min, taking out, and performing vacuum drying to obtain the pretreated continuous glass fiber cloth. The silane coupling agent B is KH-843, and the mass ratio of the silane coupling agent B to the absolute ethyl alcohol to the deionized water is 5: 12: 2; the bath ratio is 1: 10.
soaking the pretreated continuous glass fiber cloth into the graphene dispersion liquid for 15min, adding gamma-mercaptopropyl-trimethoxysilane, continuing stirring for 25min, taking out and vacuum-drying to obtain graphene oxide-loaded fiber cloth; the bath ratio is 1: 10. the mol ratio of the graphene oxide to the gamma-mercaptopropyl-trimethoxysilane is 1: 4.
mixing an epoxy monomer containing allyl with toluene to obtain an epoxy monomer solution; the concentration of the epoxy monomer solution is 4 g/L; soaking the fiber cloth loaded with graphene oxide-silicon dioxide into an epoxy monomer solution, stirring and reacting for 35min under a nitrogen environment, wherein the reaction temperature is 90 ℃, adding azobisisobutyronitrile, continuing to react for 11h, taking out after the reaction, washing and drying to obtain modified glass fiber cloth; the using amount of the azodiisobutyronitrile is 1 wt% of the epoxy monomer; the mass ratio of the graphene oxide-silicon dioxide loaded fiber cloth to the epoxy monomer is 1: 8.
(3) mixing epoxy resin and an epoxy monomer containing allyl, adding a curing agent, and uniformly mixing to obtain a glue solution; coating glue solution on two sides of modified glass fiber cloth, and curing to form a prepreg; the coating amount was 250g/m 2 . The mass ratio of the epoxy resin to the allyl-containing epoxy monomer to the curing agent is 5: 1: 1.5; the curing agent is polyamide 650.
And (4) stacking four layers of prepregs from top to bottom, and performing hot-pressing compounding to obtain a finished product.
Detection experiment:
1. the cover plate samples prepared in examples 1 to 4 and comparative examples 1 to 8, which had dimensions of 10cm × 8cm, were immersed in distilled water at normal temperature for 7 days, taken out and then wiped to remove surface moisture, and the water absorption was calculated by weighing and recording the samples before and after immersion.
2. Taking the cover plate samples prepared in examples 1-4 and comparative examples 1-8, and detecting the bending strength according to GB/T9341-2008 'determination of plastic bending property'; after the test, the plate was left at 140 ℃ in a 100% humidity environment for 7 days, and the bending strength was again tested.
3. The cover plate samples prepared in examples 1 to 4 and comparative examples 1 to 8 were taken, treated at 250 ℃ for 3 hours, and the change in the appearance thereof was observed.
Item Flexural Strength (MPa) Flexural Strength after standing (MPa) Water absorption% Appearance (250 ℃, 3h)
Example 1 627 514 0.8％ No delamination and no discoloration
Example 2 631 517 0.7％ No delamination and no discoloration
Example 3 623 511 0.7％ No delamination and no discoloration
Example 4 646 544 0.6％ No delamination and no discoloration
Comparative example 1 628 502 0.9％ /
Comparative example 2 626 476 1.6％ /
Comparative example 3 617 495 0.7％ /
Comparative example 4 611 476 0.9％ /
Comparative example 5 602 469 1.1％ /
Comparative example 6 596 458 1.4％ /
Comparative example 7 593 421 2.1％ /
Comparative example 8 588 474 0.7％ /
And (4) conclusion: the scheme discloses a production process of a composite mobile phone cover with textures, the process is reasonable in design and simple in operation, the prepared composite mobile phone cover plate has excellent strength and mechanical property, the surface of the composite mobile phone cover plate is excellent in waterproof and moisture-proof performance, and the composite mobile phone cover plate is excellent in high-temperature resistance and has high practicability.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The utility model provides a production technology of compound wrench cover of band texture which characterized in that: the method comprises the following steps:
mixing epoxy resin and an epoxy monomer containing allyl, adding a curing agent, and uniformly mixing to obtain a glue solution; coating glue solution on two sides of modified glass fiber cloth, and curing to form a prepreg;
and taking a plurality of layers of prepreg to stack from top to bottom, placing a texture film on the upper surface, wherein the texture film comprises a PET (polyethylene terephthalate) bottom layer and a UV (ultraviolet) adhesive layer with texture patterns, contacting the UV adhesive layer with the prepreg, performing hot-pressing compounding, and removing the PET bottom layer to obtain the mobile phone cover with texture.
2. The process of claim 1 for producing a textured composite wrench cover, comprising: the preparation steps of the modified glass fiber cloth are as follows:
(1) mixing graphene oxide and deionized water, stirring for 20-30 min, and performing ultrasonic dispersion for 1-1.5 h to obtain a graphene dispersion liquid;
mixing a silane coupling agent A and ethanol to obtain a mixed solution; taking silicon dioxide and deionized water, ultrasonically stirring for 20-30 min, adding the mixed solution at 50-60 ℃, reacting for 1-1.5 h under heat preservation, then heating to 70-80 ℃, and carrying out heat preservation treatment for 2-2.5 h to obtain a silicon dioxide dispersion solution; the silane coupling agent A is a mixture of KH-550 and KH-560;
(2) soaking the continuous glass fiber cloth into the graphene dispersion liquid for 10-20 min, taking out and vacuum-drying; soaking in a silicon dioxide dispersion liquid, standing for 15-20 min, adjusting the pH value of the silicon dioxide dispersion liquid to 8-9, heating to 65-75 ℃, keeping the temperature for reaction for 2-3 h, adding gamma-mercaptopropyl trimethoxysilane, continuing stirring for 20-30 min, taking out, and drying in vacuum to obtain graphene oxide-silicon dioxide loaded fiber cloth;
mixing an epoxy monomer containing allyl with toluene to obtain an epoxy monomer solution; soaking the fiber cloth loaded with graphene oxide-silicon dioxide into an epoxy monomer solution, stirring and reacting for 30-40 min under a nitrogen environment, wherein the reaction temperature is 85-90 ℃, adding azobisisobutyronitrile, continuing to react for 10-12 h, taking out after reaction, washing and drying to obtain the modified glass fiber cloth.
3. The process of claim 2 for producing a textured composite wrench cover, comprising: the preparation method of the epoxy monomer containing allyl comprises the following steps:
s1: dissolving a diphenol monomer in absolute ethyl alcohol, adding anhydrous potassium carbonate, heating to 80-85 ℃, stirring for reaction for 1-1.5 hours, slowly dropwise adding allyl bromide during reaction, continuing to react for 6-8 hours, collecting a product after the reaction, sequentially washing with absolute ethyl alcohol and deionized water, drying in vacuum, heating to 170-180 ℃ under a nitrogen atmosphere, carrying out heat preservation treatment for 20-30 min, continuing to heat to 210-215 ℃, and carrying out heat preservation reaction for 1.5-2 hours to obtain a monomer containing allyl; the diphenol monomer comprises 3-fluorobiphenyl-4, 4 '-diphenol, 4' -amino-4-diphenol and diphenol;
s2: taking a monomer containing allyl, epoxy chloropropane, benzyltriethylammonium chloride and dioxane, mixing and stirring for 20-30 min, heating to 90-95 ℃, stirring and reacting for 4-5 h, collecting a product after the reaction, mixing the product with toluene, dripping a sodium hydroxide solution at 85-90 ℃, continuing to react for 4-5 h, washing with deionized water after the reaction, and drying in vacuum to obtain the epoxy monomer containing allyl.
4. The process of claim 3 for producing a textured composite wrench cover, wherein: in step S1, the molar ratio of 3-fluorobiphenyl-4, 4 '-diol, 4' -amino-4-biphenol and biphenol is 1: 1: 1; the molar ratio of the diphenol monomer to the anhydrous potassium carbonate to the allyl bromide is 1: (2.5-3): (4-5).
5. The process of claim 3 for producing a textured composite wrench cover, comprising: in step S2, the molar ratio of the allyl-containing monomer to epichlorohydrin to benzyltriethylammonium chloride is 1: 4: 0.5.
6. the process of claim 2 for producing a textured composite wrench cover, comprising: in the step (1), the molar ratio of KH-550 to KH-560 is 3: 1; the mass ratio of the silicon dioxide to the silane coupling agent A is 10: 1, the molar ratio of the KH-550 to the gamma-mercaptopropyltrimethoxysilane is 1: 3.
7. the process of claim 2 for producing a textured composite wrench cover, comprising: in the step (2), the continuous glass fiber cloth is pretreated, and the method specifically comprises the following steps: taking a silane coupling agent B, absolute ethyl alcohol and deionized water, and carrying out ultrasonic dispersion for 20-30 min to obtain a silane coupling agent solution; and soaking the continuous glass fiber cloth into a silane coupling agent solution for 20-30 min, taking out, and performing vacuum drying to obtain the pretreated continuous glass fiber cloth.
8. The process of claim 7 for producing a textured composite wrench cover, comprising: the silane coupling agent B is KH-843.
9. The process of claim 1 for producing a textured composite wrench cover, comprising: the mass ratio of the epoxy resin, the epoxy monomer containing allyl and the curing agent is 5: 1: 1.5; the curing agent is polyamide 650.
10. A handset cover prepared by the process for producing a textured composite wrench cover according to any one of claims 1 to 9.
CN202210536606.1A 2022-05-17 2022-05-17 Composite board mobile phone cover with textures and production process thereof Active CN114987024B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210536606.1A CN114987024B (en) 2022-05-17 2022-05-17 Composite board mobile phone cover with textures and production process thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210536606.1A CN114987024B (en) 2022-05-17 2022-05-17 Composite board mobile phone cover with textures and production process thereof

Publications (2)

Publication Number Publication Date
CN114987024A true CN114987024A (en) 2022-09-02
CN114987024B CN114987024B (en) 2023-10-03

Family

ID=83027581

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210536606.1A Active CN114987024B (en) 2022-05-17 2022-05-17 Composite board mobile phone cover with textures and production process thereof

Country Status (1)

Country Link
CN (1) CN114987024B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115464950A (en) * 2022-10-17 2022-12-13 江西德思恩新材料有限公司 Composite material cover plate and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103770390A (en) * 2014-01-09 2014-05-07 广州金发碳纤维新材料发展有限公司 Continuous fiber ultrathin composite material sheet with different surface patterns and preparation method and application of sheet
US20160002417A1 (en) * 2013-02-06 2016-01-07 Changzhou Loong Top New Materials Technology Co., Ltd Toughened epoxy resin/glass fiber prepreg and preparation method thereof
CN113061275A (en) * 2021-03-23 2021-07-02 惠州市纵胜电子材料有限公司 Production process of spraying plate for main battery cover of mobile phone
CN113681935A (en) * 2021-08-13 2021-11-23 惠州市众力电子科技有限公司 Production process and application of transparent 3D glass fiber board with textures

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160002417A1 (en) * 2013-02-06 2016-01-07 Changzhou Loong Top New Materials Technology Co., Ltd Toughened epoxy resin/glass fiber prepreg and preparation method thereof
CN103770390A (en) * 2014-01-09 2014-05-07 广州金发碳纤维新材料发展有限公司 Continuous fiber ultrathin composite material sheet with different surface patterns and preparation method and application of sheet
CN113061275A (en) * 2021-03-23 2021-07-02 惠州市纵胜电子材料有限公司 Production process of spraying plate for main battery cover of mobile phone
CN113681935A (en) * 2021-08-13 2021-11-23 惠州市众力电子科技有限公司 Production process and application of transparent 3D glass fiber board with textures

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
戴雪岩: "烯丙基功能化环氧树脂的设计、制备及性能研究", 中国博士学位论文全文数据库（电子期刊）, pages 016 - 209 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115464950A (en) * 2022-10-17 2022-12-13 江西德思恩新材料有限公司 Composite material cover plate and preparation method thereof

Also Published As

Publication number Publication date
CN114987024B (en) 2023-10-03

Similar Documents

Publication Publication Date Title
CN110016807A (en) A kind of surface modifying method of carbon fiber surface functionalization
CN114987024A (en) Composite wrench cover with textures and production process thereof
CN111531658B (en) Preparation method of impregnated bond paper facing formaldehyde-free artificial board
CN103556461A (en) Electronic grade glass fiber cloth surface treating agent and method
CN101781444A (en) Method for preparing rare-earth-modified glass-fiber epoxy-resin composite materials
CN107553936B (en) A method of it carries out preparing fiberglass using vacuum diversion
US3493461A (en) Glass fiber reinforced polyvinyl chloride resin article and process therefor
CN115926587A (en) Anti-corrosion wear-resistant coating and preparation method thereof
CN109679511A (en) A kind of rapid curing glue film and preparation method thereof
CN114030250B (en) High-elasticity-modulus high-strength glass fiber laminated board and preparation method thereof
CN116590964A (en) Low-formaldehyde wear-resistant antibacterial composite impregnated paper and preparation method thereof
CN103551053B (en) A kind of preparation method of hydrophobic composite membrane
CN117468268B (en) Water-blocking paper bag and preparation method and application thereof
CN112045808A (en) Bionic super-hydrophobic wood and preparation method thereof
CN109836557A (en) Toughened hydrophobic epoxy resin and preparation method thereof
CN110202890B (en) Thin type cracking-resistant decorative plate
CN110408066A (en) Environment protection damp-proof high abrasion finishing material and its preparation method and application
CN111719239A (en) High-strength anti-aging glass fiber cotton felt
CN114670294B (en) High-strength ecological plate and manufacturing process
CN115256577A (en) Method for improving dimensional stability and strength of wood
CN106700102A (en) Polyphenylene sulfide reinforced composite material and preparing method thereof
CN115160608B (en) Basalt fiber reinforced polyether-ether-ketone based composite material, and preparation method and application thereof
CN101838442A (en) Preparation method of rare earth modified glass fiber epoxy resin composite material
CN218149404U (en) Anti-yellowing melamine UV (ultraviolet) plate with high adhesive force
CN114103156B (en) System and method for producing high-elasticity-modulus high-strength glass fiber laminated board

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
CP03 Change of name, title or address

Address after: Zongsheng Industrial Park, Dongfeng Village, Dongfeng Village, Xinwei Town, Huiyang District, Huizhou City, Guangdong Province, 516000

Patentee after: Guangdong Zongsheng New Materials Co.,Ltd.

Address before: 516200 Zongsheng Industrial Park, sub group 2, Dongfeng Village, Xinwei Town, Huiyang District, Huizhou City, Guangdong Province

Patentee before: HUIZHOU ZONGSHENG ELECTRONIC MATERIAL Co.,Ltd.

CP03 Change of name, title or address