CN113928048B - Metal frame connecting structure and application thereof - Google Patents
Metal frame connecting structure and application thereof Download PDFInfo
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- CN113928048B CN113928048B CN202111123611.1A CN202111123611A CN113928048B CN 113928048 B CN113928048 B CN 113928048B CN 202111123611 A CN202111123611 A CN 202111123611A CN 113928048 B CN113928048 B CN 113928048B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C3/00—Processes, not specifically provided for elsewhere, for producing ornamental structures
- B44C3/12—Uniting ornamental elements to structures, e.g. mosaic plates
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G1/00—Mirrors; Picture frames or the like, e.g. provided with heating, lighting or ventilating means
- A47G1/06—Picture frames
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Abstract
The invention relates to the technical field of decorative frames and discloses a metal frame connecting structure and application thereof, wherein the metal frame connecting structure comprises a frame body and metal connecting sheets for connecting two ends of the frame body; the frame comprises a frame body and is characterized in that the inner side of the frame body is provided with a mounting groove, the metal connecting sheet is positioned in the mounting groove, and two ends of the metal connecting sheet are respectively bonded with the bottoms of the mounting grooves at two ends of the frame body through an adhesive. According to the invention, the two ends of the metal frame are connected into the frame through the metal connecting sheet, so that the connection strength is ensured and the cracking of the connection position is avoided while the smoothness and the attractiveness of the connection position are ensured.
Description
Technical Field
The invention relates to the technical field of decorative frames, in particular to a metal frame connecting structure and application thereof.
Background
With the improvement of living standard and the progress and development of science and technology, the demand of people on the diversity and the aesthetic property of decorative frame products such as mirror frames, picture frames, photo frames and the like is increasingly improved, and various frame products with different shapes such as circles, polygons and the like are widely applied to the decoration of products such as decorative pictures, mirrors and the like. Because metal materials such as aluminum alloy and the like have the advantages of light weight, wear resistance, corrosion resistance, high strength and the like, frame products in the current market for picture frames or other fields are generally made of metal profiles.
When a conventional frame product is manufactured, a plurality of metal profiles are generally connected together, or two ends of one metal profile are butted to form a frame, and two ends of the plurality of metal profiles or two ends of one metal profile are generally connected in a welding manner. For example, "an aluminum frame bathroom mirror" disclosed in chinese patent literature, publication No. CN108308964A, includes: the three-side welding frame, the buckle frame edge connected with the three-side frame and the sealing strip of the aluminum alloy frame edge.
However, when the metal section is welded into a frame, the welding position is uneven and scars exist, and the connecting position is also easy to deform by heat, so that the decorative effect of the frame products is influenced. Therefore, new connection methods are needed to meet the consumers' demands for higher and higher aesthetics of the decorative frame.
Disclosure of Invention
The invention provides a metal frame connecting structure and application thereof, aiming at overcoming the problems that when a metal frame is welded into a frame, the welding position is uneven, scars exist, and the connecting position is easy to deform by heat so as to influence the decorative effect of frame products in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a metal frame connecting structure comprises a frame body and metal connecting sheets for connecting two ends of the frame body; the inner side of the frame body is provided with an installation groove, the metal connecting sheet is positioned in the installation groove, and two ends of the metal connecting sheet are respectively bonded with the bottoms of the installation grooves at two ends of the frame body through an adhesive; the two ends of the frame body are attached to each other.
According to the invention, the two ends of the frame body are connected through the metal connecting sheets positioned in the mounting grooves on the inner side of the frame body, and a built-in connection mode is adopted, so that scars generated when the seams at the two ends of the frame body are welded can be avoided, and after the frame body is connected into a frame, the metal connecting sheets can not be seen from the front side of the frame, and the decorative effect of the front side of the frame can not be influenced; meanwhile, the metal connecting sheets are high in connecting strength, the joints are not prone to cracking and thermal deformation, and the service life of the frame is prolonged. Therefore, the invention improves the aesthetic property of the joint while ensuring the connection strength of the joint of the metal frame.
Preferably, both ends of the metal connecting sheet are respectively provided with a flow guide hole. The flow guide holes are formed in the two ends of the metal connecting sheet, so that the adhesive can be guided when being coated, the adhesive is uniformly distributed, and the adhesive is prevented from overflowing from the joint when being coated on the surface of the metal connecting sheet too much to affect the attractiveness of the joint.
Preferably, the metal connecting sheet has a length of 20 to 40mm and a thickness of 0.4 to 0.8mm. The length and the thickness of the metal connecting sheet are limited, so that the connecting strength of the metal connecting sheet to the frame body can be ensured, and the phenomenon that the connection of the frame body and the decorative main bodies such as the mirror surface and the painting core is influenced due to the overlong and over-thick metal connecting sheet can be avoided.
Preferably, the adhesive is a two-component epoxy resin adhesive, and the two-component epoxy resin adhesive comprises a component A and a component B in a mass ratio of 2-3; the component A comprises the following raw materials in parts by weight: 90-100 parts of bisphenol A type epoxy resin and 3-5 parts of diluent; the component B comprises the following raw materials: 80-90 parts of phytic acid and POSS modified amine curing agent, 3-5 parts of curing accelerator and 8-10 parts of toluene.
Because the epoxy resin adhesive has the characteristics of strong adhesive force, high mechanical strength of materials, good chemical resistance, small curing shrinkage and the like, the epoxy resin adhesive is selected for bonding the frame body and the metal connecting sheet. However, the cured epoxy resin adhesive usually has the defects of brittleness, poor impact resistance and peeling strength, easy cracking and the like, and the seam is easy to crack under the action of external force when the cured epoxy resin adhesive is used for adhering a frame body and a metal connecting sheet. Meanwhile, a cross-linking structure can be formed after the epoxy resin is cured, tiny pores can exist in the adhesive layer, corrosive media such as water, oxygen and the like can penetrate into the adhesive layer through the pores in the using process of the frame and contact with the frame body and the metal connecting sheet to corrode the surfaces of the frame body and the metal connecting sheet, corrosion products are accumulated between the adhesive layer and the metal layer, the adhesive coating is enabled to form bubbling, cracking and peeling gradually, and the service life of the frame is affected.
Therefore, the curing agent of the epoxy resin adhesive is modified by adopting phytic acid and POSS, the POSS is a nano-scale cage-shaped structure compound, the internal inorganic framework consisting of Si-O endows the compound with high rigidity, heat resistance and chemical stability, and the compound can better absorb external energy, obviously improve the toughness of the epoxy resin and improve the impact resistance and peel strength of the adhesive when added into the epoxy resin. The phytic acid is a metal polydentate chelating agent, and can be added into the adhesive to effectively form a layer of protective film on the surfaces of the frame body and the metal connecting sheet through chelation, so that the contact between a corrosive medium and a metal matrix is prevented, and the reduction of bonding strength caused by corrosion and the influence on the service life of the frame are avoided. However, because the compatibility between POSS and phytic acid and the epoxy resin matrix is poor, when the POSS and the phytic acid are directly added into the epoxy resin, the toughening and corrosion prevention effects on the adhesive are poor; according to the invention, the curing agent is modified by POSS and phytic acid, and the POSS and the phytic acid after the curing agent is mixed with the epoxy resin can be connected in the crosslinked resin matrix along with the reaction of the amine curing agent and the epoxy resin, so that the compatibility with the resin matrix is improved, and the adhesive can obtain better toughening and anticorrosion effects.
Preferably, the bisphenol a epoxy resin is epoxy resin E44 or epoxy resin E51; the diluent is selected from one or more of butyl glycidyl ether, benzyl glycidyl ether and 1, 4-butanediol diglycidyl ether; the curing accelerator is an imidazole accelerator.
Preferably, the preparation method of the phytic acid and POSS modified amine curing agent comprises the following steps:
(1) Adding 3-glycidyloxypropyltrimethoxysilane and aqueous solution of tetramethylammonium hydroxide into isopropanol, stirring and reacting for 5-7 h, then carrying out reduced pressure distillation to remove the isopropanol, adding toluene to dissolve the product, carrying out reflux reaction at 70-80 ℃ for 5-6 h, washing the reacted solution with saturated sodium chloride solution to be neutral, separating to obtain an organic phase, and carrying out rotary evaporation and drying to obtain epoxy group POSS;
(2) Dissolving epoxy POSS in DMF, adding ethylene glycol, stirring uniformly, adding NaOH, and stirring at 60-80 ℃ for reaction for 2-3 h; then adding triethylenetetramine, and continuing to react for 3-5 h under heat preservation; removing the solvent by rotary evaporation and drying to obtain the POSS modified amine curing agent;
(3) Dissolving POSS modified amine curing agent in dimethyl sulfoxide, adding dicyandiamide and urea, heating to 100-110 ℃ under the protection of nitrogen, then adding phytic acid aqueous solution and toluene, and stirring and reacting for 1-3 h; and precipitating the product by using absolute ethyl alcohol, washing and drying the precipitated product to obtain the phytic acid and POSS modified amine curing agent.
Firstly, preparing eight epoxy group POSS with epoxy groups at the top by using hydrolysis reaction of 3-glycidoxypropyltrimethoxysilane in the step (1); then modifying ethylene glycol and triethylenetetramine on POSS by using the reaction of epoxy group, hydroxyl and amino to make POSS have hydroxyl and amino through step (2); and (3) finally, carrying out esterification reaction on hydroxyl on POSS and phosphate groups in the phytic acid to connect the phytic acid to the POSS, and finally obtaining the phytic acid and the POSS modified amine curing agent. After the component A and the component B are mixed, the phytic acid and POSS can be connected in a crosslinked resin matrix along with the reaction of amino and epoxy, so that the compatibility with the resin matrix is improved.
Preferably, the mass fraction of the aqueous solution of tetramethylammonium hydroxide in step (1) is 5 to 8%; the addition ratio of the 3-glycidoxypropyltrimethoxysilane to the aqueous solution of tetramethylammonium hydroxide to the isopropanol is 90-100g.
Preferably, the mass-to-volume ratio of the epoxy POSS to the DMF in the step (2) is 1g; the mass ratio of NaOH, glycol, triethylene tetramine and epoxy POSS added is 1-3.
Preferably, the mass ratio of the POSS modified amine curing agent to the dicyandiamide to the urea in the step (3) is (10); the mass fraction of the phytic acid aqueous solution is 20-40%, and the mass ratio of the phytic acid in the phytic acid aqueous solution to the POSS modified amine curing agent is 1; the volume ratio of the phytic acid aqueous solution to the toluene is 1.
The invention also discloses an application of the metal frame connecting structure in a mirror, wherein the mirror comprises a mirror body and the metal frame connecting structure, and the edge of the mirror body is clamped in the mounting groove on the frame body.
When the mirror is installed, one end of the metal connecting sheet is firstly bonded with one end of the frame body through the adhesive, then the edge of the mirror body is clamped into the installing groove on the frame body until the two ends of the frame body are in butt joint, then the other end of the metal connecting sheet is coated with the adhesive and then placed into the installing groove of the frame body, the joint of the frame body is pressed, and the mirror is obtained after the adhesive is cured. The installation operation is simple and convenient, and the junction of metal frame is level and smooth, pleasing to the eye, is difficult for the fracture.
Preferably, the edge of the mirror body is bonded to the mounting groove by an adhesive. The production method of the mirror body generally comprises the steps of plating a layer of metal aluminum or metal silver on the surface of glass to serve as a reflecting layer, and then coating a layer of protective paint on the reflecting layer to prevent the metal layer from being chemically corroded and physically damaged; however, when the periphery of the mirror body is cut, ground, polished and the like, the protective paint near the cut part is easy to fall off and is difficult to repair, so that the metal layer around the mirror body is exposed and is easy to oxidize and discolor by air, and the use attractiveness of the mirror is seriously affected by the oxidized and blackened edge. Therefore, when the metal frame is used as a decorative frame of a mirror, the two-component epoxy resin binder can be coated in the mounting groove of the frame body, then the edge of the mirror body is clamped in the mounting groove, the edge of the mirror body is bonded with the frame body through the adhesive, the metal layer around the mirror body can be protected while the connection between the mirror body and the metal frame is strengthened, the edge of the mirror body is prevented from being oxidized and blackened, and the service life of the mirror is prolonged.
Therefore, the invention has the following beneficial effects:
(1) The two ends of the metal frame are connected through the metal connecting sheets positioned in the mounting grooves on the inner side of the metal frame, and a built-in connection mode is adopted, so that scars generated when the joints at the two ends of the metal frame are welded can be avoided, and after the metal frame is connected into a frame, the metal connecting sheets can not be seen from the front side of the frame, and the decorative effect of the front side of the frame can not be influenced;
(2) The metal connecting sheets have high connecting strength, the joints are not easy to crack and deform due to heat, and the service life of the frame is prolonged;
(3) The epoxy resin adhesive is modified by POSS and phytic acid, so that the impact resistance and the peel strength of the adhesive are improved, the bonding strength reduction caused by the corrosion of a metal frame and a metal connecting piece can be effectively prevented, and the service life of the frame is prolonged; when the decorative frame is used for the decorative frame of the mirror, the oxidation and corrosion discoloration of the edge of the mirror body can be prevented.
Drawings
Fig. 1 is a schematic view of a connection structure of a frame body and a metal connecting sheet in embodiment 1.
Fig. 2 is a partially enlarged view of a portion a in fig. 1.
Fig. 3 is a sectional view of the joint of the metal bezel and the metal connecting piece in embodiment 1.
Fig. 4 is a plan view of a metal connecting sheet in embodiment 1.
In the figure: 1 frame body, 101 mounting groove, 2 metal connecting sheets, 201 water conservancy diversion hole, 3 adhesives.
Detailed Description
The invention is further described with reference to the following detailed description and accompanying drawings.
Example 1:
as shown in figure 1, a metal frame connecting structure comprises an oval frame body 1 and metal connecting pieces 2 used for connecting two ends of the frame body, wherein the frame body is an aluminum alloy frame, and the metal connecting pieces are aluminum sheets. As shown in fig. 2 and 3, the inner side of the frame body is provided with a mounting groove 101, the metal connecting sheet is positioned in the mounting groove, two ends of the metal connecting sheet are respectively bonded with the bottoms of the mounting grooves at two ends of the frame body through an adhesive 3, and two ends of the frame body are attached to each other; the thickness of two side walls of the mounting groove is 0.8mm respectively, the distance between the two side walls is 6mm, and the depth of the mounting groove is 5.7mm; the metal connecting sheet is rectangular, the length is 36mm, the thickness is 0.8mm, and the width is 5mm. As shown in fig. 4, two ends of the metal connecting sheet are respectively provided with two diversion holes 201, and the diameter of each diversion hole is 3mm.
The adhesive is a two-component epoxy resin adhesive and comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 2.5; the component A comprises the following raw materials in parts by weight: 95 parts of an epoxy resin E51,4 parts of a diluent 1, 4-butanediol diglycidyl ether; the component B comprises the following raw materials: 85 parts of phytic acid and POSS modified amine curing agent, 4 parts of dimethyl imidazole and 9 parts of toluene.
The preparation method of the phytic acid and POSS modified amine curing agent comprises the following steps:
(1) Adding 3-glycidoxypropyltrimethoxysilane and 6wt% of aqueous solution of tetramethylammonium hydroxide into isopropanol, wherein the addition ratio of the 3-glycidoxypropyltrimethoxysilane to the aqueous solution of the tetramethylammonium hydroxide to the isopropanol is 95g; stirring for reacting for 6h, then carrying out reduced pressure distillation to remove isopropanol, adding toluene to dissolve the product, carrying out reflux reaction at 75 ℃ for 5.5h, washing the reacted solution to neutrality by using a saturated sodium chloride solution, separating to obtain an organic phase, and carrying out rotary evaporation and drying to obtain epoxy group POSS;
(2) Dissolving epoxy POSS in DMF, wherein the mass-to-volume ratio of epoxy POSS to DMF is 1g; adding ethylene glycol, stirring uniformly, adding NaOH, and stirring at 70 ℃ for reaction for 2.5 hours; then adding triethylenetetramine, and continuing to perform heat preservation reaction for 4 hours, wherein the mass ratio of the added NaOH, ethylene glycol, triethylenetetramine to epoxy group POSS is 2.8; removing the solvent by rotary evaporation and drying to obtain the POSS modified amine curing agent;
(3) Dissolving a POSS modified amine curing agent in dimethyl sulfoxide, and adding dicyandiamide and urea, wherein the mass ratio of the POSS modified amine curing agent to the dicyandiamide to the urea is 10.4; heating to 105 ℃ under the protection of nitrogen, and then adding 30wt% of phytic acid aqueous solution and toluene, wherein the mass ratio of the phytic acid in the phytic acid aqueous solution to the POSS modified amine curing agent is 1; the volume ratio of the phytic acid aqueous solution to the toluene is 1; and precipitating the product by using absolute ethyl alcohol, washing and drying the precipitated product to obtain the phytic acid and POSS modified amine curing agent.
Example 2:
the utility model provides a metal frame connection structure, includes oval-shaped frame body and is used for connecting the metal connection piece at frame body both ends, and the frame body adopts the aluminum alloy frame, and the metal connection piece adopts the aluminum sheet. The inner side of the frame body is provided with an installation groove, the metal connecting sheet is positioned in the installation groove, two ends of the metal connecting sheet are respectively bonded with the bottoms of the installation grooves at two ends of the frame body through an adhesive, and two ends of the frame body are attached to each other; the thickness of two side walls of the mounting groove is 0.8mm respectively, the distance between the two side walls is 6mm, and the depth of the mounting groove is 5.7mm; the metal connecting sheet is rectangular, the length is 20mm, the thickness is 0.8mm, and the width is 5mm. Two ends of the metal connecting sheet are respectively provided with two diversion holes, and the diameter of each diversion hole is 3mm.
The adhesive is a two-component epoxy resin adhesive and comprises a component A and a component B in a mass ratio of 2; the component A comprises the following raw materials in parts by weight: 90 parts of epoxy resin E51,3 parts of diluent 1, 4-butanediol diglycidyl ether; the component B comprises the following raw materials: 80 parts of phytic acid and POSS modified amine curing agent, 3 parts of dimethyl imidazole and 8 parts of toluene.
The preparation method of the phytic acid and POSS modified amine curing agent comprises the following steps:
(1) Adding 3-glycidoxypropyltrimethoxysilane and a 5wt% aqueous solution of tetramethylammonium hydroxide into isopropanol, wherein the addition ratio of the 3-glycidoxypropyltrimethoxysilane to the aqueous solution of the tetramethylammonium hydroxide to the isopropanol is 9045g; stirring for reacting for 5h, then carrying out reduced pressure distillation to remove isopropanol, adding toluene to dissolve the product, carrying out reflux reaction at 70 ℃ for 6h, washing the reacted solution with a saturated sodium chloride solution to neutrality, separating to obtain an organic phase, and carrying out rotary evaporation and drying to obtain epoxy group POSS;
(2) Dissolving epoxy POSS in DMF, wherein the mass-volume ratio of the epoxy POSS to the DMF is 1g; adding ethylene glycol, stirring uniformly, adding NaOH, and stirring at 60 ℃ for reaction for 3 hours; then adding triethylenetetramine, and continuing to perform heat preservation reaction for 5 hours, wherein the mass ratio of the added NaOH, ethylene glycol, triethylenetetramine to epoxy group POSS is 1.5; removing the solvent by rotary evaporation and drying to obtain the POSS modified amine curing agent;
(3) Dissolving a POSS modified amine curing agent in dimethyl sulfoxide, and adding dicyandiamide and urea, wherein the mass ratio of the POSS modified amine curing agent to the dicyandiamide to the urea is 10.3; heating to 100 ℃ under the protection of nitrogen, and then adding 20wt% of phytic acid aqueous solution and toluene, wherein the mass ratio of the phytic acid in the phytic acid aqueous solution to the POSS modified amine curing agent is 1; the volume ratio of the phytic acid aqueous solution to the toluene is 1; and precipitating the product by using absolute ethyl alcohol, washing and drying the precipitated product to obtain the phytic acid and POSS modified amine curing agent.
Example 3:
the utility model provides a metal frame connection structure, includes oval-shaped frame body and is used for connecting the metal connection piece at frame body both ends, and the frame body adopts the aluminum alloy frame, and metal connection piece adopts the aluminum sheet. The inner side of the frame body is provided with an installation groove, the metal connecting sheet is positioned in the installation groove, two ends of the metal connecting sheet are respectively bonded with the bottoms of the installation grooves at two ends of the frame body through an adhesive, and two ends of the frame body are attached to each other; the thickness of two side walls of the mounting groove is 0.8mm respectively, the distance between the two side walls is 6mm, and the depth of the mounting groove is 5.7mm; the metal connecting sheet is rectangular, the length is 40mm, the thickness is 0.4mm, and the width is 5mm. Two ends of the metal connecting sheet are respectively provided with two diversion holes, and the diameter of each diversion hole is 3mm.
The adhesive is a two-component epoxy resin adhesive and comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 3; the component A comprises the following raw materials in parts by weight: 100 parts of epoxy resin E51,5 parts of diluent 1, 4-butanediol diglycidyl ether; the component B comprises the following raw materials: 90 parts of phytic acid and POSS modified amine curing agent, 5 parts of dimethyl imidazole and 10 parts of toluene.
The preparation method of the phytic acid and POSS modified amine curing agent comprises the following steps:
(1) Adding 3-glycidoxypropyltrimethoxysilane and an aqueous solution of 8wt% of tetramethylammonium hydroxide into isopropanol, wherein the addition ratio of the 3-glycidoxypropyltrimethoxysilane to the aqueous solution of the tetramethylammonium hydroxide to the isopropanol is 10035g; stirring for reacting for 6 hours, then carrying out reduced pressure distillation to remove isopropanol, then adding toluene to dissolve the product, carrying out reflux reaction for 5 hours at 80 ℃, washing the reacted solution with a saturated sodium chloride solution to be neutral, separating to obtain an organic phase, and carrying out rotary evaporation and drying to obtain epoxy group POSS;
(2) Dissolving epoxy POSS in DMF, wherein the mass-to-volume ratio of epoxy POSS to DMF is 1g; adding ethylene glycol, stirring uniformly, adding NaOH, and stirring at 80 ℃ for reaction for 2 hours; then adding triethylenetetramine, and continuing to perform heat preservation reaction for 3 hours, wherein the mass ratio of the added NaOH, ethylene glycol, triethylenetetramine to epoxy group POSS is 3; removing the solvent by rotary evaporation and drying to obtain the POSS modified amine curing agent;
(3) Dissolving a POSS modified amine curing agent in dimethyl sulfoxide, and adding dicyandiamide and urea, wherein the mass ratio of the POSS modified amine curing agent to the dicyandiamide to the urea is 10.5; heating to 110 ℃ under the protection of nitrogen, and then adding 40wt% of phytic acid aqueous solution and toluene, wherein the mass ratio of the phytic acid in the phytic acid aqueous solution to the POSS modified amine curing agent is 1; the volume ratio of the phytic acid aqueous solution to the toluene is 1; and precipitating the product by using absolute ethyl alcohol, washing and drying the precipitated product to obtain the phytic acid and POSS modified amine curing agent.
Comparative example 1 (without POSS and phytic acid addition):
the metal bezel connection structure in comparative example 1 is the same as that in example 1; the used double-component epoxy resin adhesive comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 2.5; the component A comprises the following raw materials in parts by weight: 95 parts of epoxy resin E51,4 parts of diluent 1, 4-butanediol diglycidyl ether; the component B comprises the following raw materials: 30 parts of triethylenetetramine, 4 parts of dimethylimidazole and 9 parts of toluene.
Comparative example 2 (no phytic acid added):
the metal bezel connection structure in comparative example 2 is the same as that in example 1; the used two-component epoxy resin adhesive comprises a component A and a component B in a mass ratio of 2.5; the component A comprises the following raw materials in parts by weight: 95 parts of epoxy resin E51,4 parts of diluent 1, 4-butanediol diglycidyl ether; the component B comprises the following raw materials: 85 parts of POSS modified amine curing agent, 4 parts of dimethyl imidazole and 9 parts of toluene.
The preparation method of the POSS modified amine curing agent comprises the following steps:
(1) Adding 3-glycidoxypropyltrimethoxysilane and 6wt% of aqueous solution of tetramethylammonium hydroxide into isopropanol, wherein the addition ratio of the 3-glycidoxypropyltrimethoxysilane to the aqueous solution of the tetramethylammonium hydroxide to the isopropanol is 95g; stirring for reacting for 6h, then carrying out reduced pressure distillation to remove isopropanol, adding toluene to dissolve the product, carrying out reflux reaction at 75 ℃ for 5.5h, washing the reacted solution to neutrality by using a saturated sodium chloride solution, separating to obtain an organic phase, and carrying out rotary evaporation and drying to obtain epoxy group POSS;
(2) Dissolving epoxy POSS in DMF, wherein the mass-to-volume ratio of epoxy POSS to DMF is 1g; adding triethylenetetramine, stirring uniformly, adding NaOH, and stirring at 70 ℃ for reacting for 6h; the mass ratio of the added NaOH, the added triethylenetetramine and the added epoxy POSS is 2; and (4) performing rotary evaporation to remove the solvent, and drying to obtain the POSS modified amine curing agent.
Comparative example 3 (phytic acid directly blended with curing agent):
the metal bezel connection structure in comparative example 3 is the same as that in example 1; the used two-component epoxy resin adhesive comprises a component A and a component B in a mass ratio of 2.5; the component A comprises the following raw materials in parts by weight: 95 parts of epoxy resin E51,4 parts of diluent 1, 4-butanediol diglycidyl ether; the component B comprises the following raw materials: 7 parts of phytic acid, 78 parts of POSS modified amine curing agent, 4 parts of dimethyl imidazole and 9 parts of toluene.
The preparation method of the POSS modified amine curing agent comprises the following steps:
(1) Adding 3-glycidoxypropyltrimethoxysilane and 6wt% of aqueous solution of tetramethylammonium hydroxide into isopropanol, wherein the addition ratio of the 3-glycidoxypropyltrimethoxysilane to the aqueous solution of the tetramethylammonium hydroxide to the isopropanol is 95g; stirring for reacting for 6h, then carrying out reduced pressure distillation to remove isopropanol, adding toluene to dissolve the product, carrying out reflux reaction at 75 ℃ for 5.5h, washing the reacted solution to neutrality by using a saturated sodium chloride solution, separating to obtain an organic phase, and carrying out rotary evaporation and drying to obtain epoxy group POSS;
(2) Dissolving epoxy POSS in DMF, wherein the mass-volume ratio of the epoxy POSS to the DMF is 1g; adding triethylenetetramine, stirring uniformly, adding NaOH, and stirring at 70 ℃ for reacting for 6h; the mass ratio of the added NaOH to the added triethylenetetramine to the added epoxy POSS is 2; and (4) performing rotary evaporation to remove the solvent, and drying to obtain the POSS modified amine curing agent.
Comparative example 4 (excessive phytic acid addition):
the metal bezel connection structure in comparative example 4 is the same as that in example 1; the components of the two-component epoxy resin adhesive used are also the same as those in example 1, wherein the preparation method of the phytic acid and POSS modified amine curing agent comprises the following steps:
(1) Adding 3-glycidoxypropyltrimethoxysilane and 6wt% of aqueous solution of tetramethylammonium hydroxide into isopropanol, wherein the addition ratio of the 3-glycidoxypropyltrimethoxysilane to the aqueous solution of the tetramethylammonium hydroxide to the isopropanol is 95g; stirring for reacting for 6h, then carrying out reduced pressure distillation to remove isopropanol, adding toluene to dissolve the product, carrying out reflux reaction at 75 ℃ for 5.5h, washing the reacted solution to neutrality by using a saturated sodium chloride solution, separating to obtain an organic phase, and carrying out rotary evaporation and drying to obtain epoxy group POSS;
(2) Dissolving epoxy POSS in DMF, wherein the mass-volume ratio of the epoxy POSS to the DMF is 1g; adding ethylene glycol, stirring uniformly, adding NaOH, and stirring at 70 ℃ for reacting for 2.5 hours; then adding triethylenetetramine, and continuing to perform heat preservation reaction for 4 hours, wherein the mass ratio of the added NaOH, ethylene glycol, triethylenetetramine to epoxy group POSS is 2; removing the solvent by rotary evaporation and drying to obtain the POSS modified amine curing agent;
(3) Dissolving a POSS modified amine curing agent in dimethyl sulfoxide, and adding dicyandiamide and urea, wherein the mass ratio of the POSS modified amine curing agent to the dicyandiamide to the urea is (10); heating to 105 ℃ under the protection of nitrogen, and then adding 30wt% of phytic acid aqueous solution and toluene, wherein the mass ratio of the phytic acid in the phytic acid aqueous solution to the POSS modified amine curing agent is 1; the volume ratio of the phytic acid aqueous solution to the toluene is 1; and precipitating the product by using absolute ethyl alcohol, washing and drying the precipitated product to obtain the phytic acid and POSS modified amine curing agent.
The two-component epoxy adhesives of the above examples and comparative examples were tested for performance according to methods in GB/T7124-2008 (rigid to rigid) and GB/T7122, with the results shown in Table 1.
Table 1: and (5) testing the performance of the two-component epoxy resin binder.
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Tensile shear Strength (MPa) | 25.1 | 23.6 | 24.2 | 9.4 | 23.6 | 22.7 | 19.8 |
| Peel strength (KN/m) | 5.2 | 4.9 | 5.0 | 2.4 | 4.8 | 4.5 | 4.4 |
Application example: the metal frame connecting structures in the embodiment and the comparative example are respectively used for manufacturing the mirror, the mirror comprises a mirror body and the metal frame connecting structure, the edge of the mirror body is clamped in the mounting groove in the frame body and is bonded with the mounting groove through a two-component epoxy resin adhesive, and the mirror body is a commercially available aluminum mirror. The manufacturing method of the mirror comprises the following steps: firstly, one end of a metal connecting sheet is bonded with one end of a frame body through a double-component epoxy resin adhesive, then the edge of the mirror body is clamped into a mounting groove on the frame body after the double-component epoxy resin adhesive is coated on the edge of the mirror body, the two ends of the frame body are butted, then the other end of the metal connecting sheet is coated with the double-component epoxy resin adhesive and then placed in the mounting groove of the frame body, so that the two ends of the frame body are attached, the seam of the frame body is pressed for 5s, and then the metal connecting sheet is cured for 12h at 80 ℃.
The mirrors prepared in the above examples and comparative examples were placed in a 5% NaOH aqueous solution, and heat-insulated at 25 ℃ for 12 hours, and the change in color of the aluminum plating layer around the mirror body was observed, and the results are shown in Table 2.
Table 2: and testing the corrosion inhibition performance of the mirror.
As can be seen from tables 1 and 2, the two-component epoxy resin adhesive in the embodiments 1 to 3 of the present invention has high tensile shear strength and peel strength, good cohesiveness, good firmness when used for bonding the frame body and the metal connecting sheet, and difficult cracking at the frame joint. The two-component epoxy resin adhesive in the embodiments 1 to 3 has good corrosion inhibition performance, and can effectively prevent the aluminum layer at the edge of the mirror body from being oxidized, corroded and discolored; and the bubbling, cracking and peeling of the adhesive layer caused by the corrosion of the metal connecting sheet and the frame body can also be avoided.
POSS and phytic acid are not added into the adhesive in the comparative example 1 to modify the amine curing agent, so that the cohesiveness of the adhesive is remarkably reduced compared with that of the adhesive in the example 1, and the risk of cracking at the frame joint is increased; and the corrosion inhibition performance to metal is reduced, and the aluminum layer at the edge of the lens body is easy to oxidize, corrode and discolor. In the comparative example 2, no phytic acid is modified on POSS, so that the corrosion inhibition of the adhesive to metal is reduced; in the comparative example 3, the phytic acid is directly added into the component B without being modified on POSS, so that the compatibility of the phytic acid and an epoxy resin matrix is poor, the bonding performance of the adhesive is reduced, and the corrosion inhibition of the adhesive to metal is also reduced; in comparative example 4, too much phytic acid modified on POSS also causes the adhesive performance of the adhesive to be reduced, probably because the steric hindrance of the phytic acid is larger, and the steric hindrance of the curing agent and the epoxy resin during reaction can be influenced by adding too much phytic acid, so that the adhesive performance of the adhesive is reduced.
Claims (8)
1. A metal frame connecting structure is characterized by comprising a frame body (1) and metal connecting sheets (2) used for connecting two ends of the frame body; the inner side of the frame body is provided with an installation groove (101), the metal connecting sheet is positioned in the installation groove, and two ends of the metal connecting sheet are respectively bonded with the bottoms of the installation grooves at two ends of the frame body through an adhesive (3); the adhesive is a two-component epoxy resin adhesive, and the two-component epoxy resin adhesive comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 2-3; the component A comprises the following raw materials in parts by weight: 90 to 100 parts of bisphenol A epoxy resin and 3 to 5 parts of a diluent; the component B comprises the following raw materials: 80-90 parts of phytic acid and POSS modified amine curing agent, 3-5 parts of curing accelerator and 8-10 parts of toluene; the preparation method of the phytic acid and POSS modified amine curing agent comprises the following steps:
(1) Adding 3-glycidyloxypropyltrimethoxysilane and a water solution of tetramethylammonium hydroxide into isopropanol, stirring and reacting for 5-7 h, then distilling under reduced pressure to remove the isopropanol, then adding toluene to dissolve the product, carrying out reflux reaction at 70-80 ℃ for 5-6 h, washing the reacted solution with a saturated sodium chloride solution to be neutral, separating to obtain an organic phase, and carrying out rotary evaporation and drying to obtain epoxy group POSS;
(2) Dissolving epoxy POSS in DMF, adding ethylene glycol, stirring uniformly, adding NaOH, and reacting at 60-80 ℃ for 2-3 h; then adding triethylenetetramine, and continuing the heat preservation reaction for 3 to 5h; removing the solvent by rotary evaporation and drying to obtain the POSS modified amine curing agent;
(3) Dissolving a POSS modified amine curing agent in dimethyl sulfoxide, adding dicyandiamide and urea, heating to 100-110 ℃ under the protection of nitrogen, adding a phytic acid aqueous solution and toluene, and stirring for reaction for 1-3 hours; and precipitating the product by using absolute ethyl alcohol, washing and drying the precipitated product to obtain the phytic acid and POSS modified amine curing agent.
2. The metal frame connecting structure of claim 1, wherein the metal connecting sheet is provided with flow guiding holes (201) at both ends thereof.
3. The metal frame connecting structure as claimed in claim 1, wherein the metal connecting sheet has a length of 20 to 40mm and a thickness of 0.4 to 0.8mm.
4. The metal frame connecting structure according to claim 1, wherein the mass fraction of the aqueous solution of tetramethylammonium hydroxide in step (1) is 5 to 8%; the ratio of the addition amounts of the 3-glycidoxypropyltrimethoxysilane to the aqueous solution of tetramethylammonium hydroxide to the addition amount of isopropanol is 90 to 100g.
5. The metal frame connecting structure of claim 1, wherein the mass-to-volume ratio of the epoxy POSS to the DMF in the step (2) is 1g; the mass ratio of NaOH, ethylene glycol, triethylenetetramine and epoxy POSS added is 1 to 3.
6. The metal frame connecting structure of claim 1, wherein the mass ratio of the POSS modified amine curing agent to the dicyandiamide to the urea in the step (3) is from 0.3 to 0.5 to 0.1 to 0.2; the mass fraction of the phytic acid aqueous solution is 20 to 40%, and the mass ratio of the phytic acid in the phytic acid aqueous solution to the POSS modified amine curing agent is 1 to 10 to 15; the volume ratio of the phytic acid aqueous solution to the toluene is 1 to 5-10.
7. The application of the metal frame connecting structure as claimed in any one of claims 1 to 6 in a mirror is characterized in that the mirror comprises a mirror body and the metal frame connecting structure, and the edge of the mirror body is clamped in a mounting groove on a frame body.
8. Use of a metal border connection according to claim 7 in a mirror, wherein the edges of the mirror body and the mounting groove are bonded by an adhesive.
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