CN115926666B - Preparation method of heat-conducting and heat-resistant EVA (ethylene vinyl acetate) film for laminated glass - Google Patents
Preparation method of heat-conducting and heat-resistant EVA (ethylene vinyl acetate) film for laminated glass Download PDFInfo
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Abstract
The invention discloses a preparation method of a heat-conducting and heat-resistant EVA film of laminated glass, which belongs to the technical field of glass laminated glue, improves heat-conducting and heat-resistant performance of the laminated glass by blending modification of composite heat-conducting and heat-resistant powder and chlorosulfonated EVA, and improves heat-conducting and heat-resistant performance of the laminated glass.
Description
Technical Field
The invention belongs to the technical field of glass interlayer adhesives, and particularly relates to a preparation method of a heat-conducting and heat-resistant EVA film for laminated glass.
Background
The remarkable heat insulation performance of the laminated glass well caters to the common practice of large-area glass curtain wall adoption of modern buildings. In the past, people had to love to be limited to the poor insulating properties of conventional glass. The laminated glass made of the plastic intermediate film has good heat insulation performance, and the difficulty is overcome. The laminated glass has a greatly improved heat transfer to the convection conduction section compared to the performance of a single glass sheet, and a reduced convection conduction heat due to a low thermal conductivity. The sun-proof and heat-insulating functions of laminated glass have been known. The electric heating glass is a glass product which can generate heat and raise temperature after being electrified, and the electric heating glass is formed by adopting a metal heat conducting film deposited on laminated glass or arranging resistance wires in an interlayer material, so that the electric heating glass has electric heating performance, and the heating temperature is controlled by a temperature regulator generally. The glass can be electrified and heated to be deiced and frosted and is in an optimal working state; for example, the CRH380AL cab window of the motor vehicle needs to be made of electric heating glass. For example, CN214164702U is also used for car, and electric heating laminated glass is used for cab window of high-speed railway train, and electric heating wire with diameter smaller than 0.01 mm is laid in the electric heating laminated glass, and the electric heating glass is electrified to prevent icing so as not to influence vision. CN201895553U discloses a double-layer black edge local silver wire electric heating laminated glass, for example, chinese patent CN201491304U, a wire-sandwiched heating laminated glass with a temperature control switch, a plurality of heating wires arranged on PVB, two ends of the plurality of heating wires connected with two bus bars, and two electrode wires connected with the bus bars, wherein a layer of heat-conducting glue is arranged at the position of the inner surface heating area of the glass near the edge, the surface temperature of the glass is raised, and the effects of defrosting, demisting and deicing are achieved. Chinese patent CN104540256a discloses a method for preparing electric heating laminated glass, but because the laminated glass has good heat insulation performance, the effect of defrosting and demisting is not good in practice, the heating temperature and heating time need to be improved, after long-time heating and use at higher temperature, the heat dissipation performance of the polymer adhesive film is not good, long-time heat aging is experienced, and the phenomena of shrinkage, degumming, yellowing and hardening of the intermediate film and glass exist at the edge, the transparency is reduced under long-term action, and the use is seriously affected. The long term temperature in PV modules is high and the heat dissipation problem is also in need of solution. In recent years, a plurality of novel membrane materials, such as EN laminated sheets, which are high-viscosity membrane materials processed by special equipment by taking ethylene and vinyl acetate copolymer as main raw materials, are developed at home and abroad, and are also called EVA laminated glass membranes. The EN film for the outdoor use of the building has ultrahigh transparency, good cohesiveness, weather resistance and impact resistance. However, EVA has poor heat resistance, and the improvement of heat conduction and heat resistance is a necessary premise for the application of the EVA clamping piece as the electric heating laminated glass. Those skilled in the art are urgent to develop a preparation method of a heat-conducting and heat-resistant EVA film for laminated glass to meet the existing application market and performance requirements.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a heat-conducting and heat-resistant EVA film for laminated glass.
A preparation method of a heat-conducting and heat-resistant EVA film for laminated glass comprises the following steps: and firstly, mixing the composite heat-conducting heat-resistant powder, the tackifier and the EVA premix according to a set proportion in a high-speed mixer at 50-60 ℃ for 15-20 min, drying at 45-50 ℃ for 1-2 h, and then rolling the extruded cast film by a film winding unit.
Further, the tackifier is one or more of disproportionated rosin, terpene phenol resin, thermoplastic phenolic resin and maleic rosin.
The reaction scheme is as follows:
further, adding 30-32 parts of gamma-aminopropyl triethoxysilane into a reaction kettle provided with a mechanical stirrer according to parts by weight, stirring in an ice-water bath at 0 ℃, dropwise adding 15-20 parts of dimethylacetamide and 25-27 parts of trichloromelamine, continuously stirring and reacting for 2.5-3 hours, raising the reaction temperature to 45-50 ℃, dropwise adding 19-19.2 parts of ethylenediamine and 10-12 parts of dimethylacetamide into the reaction kettle, reacting for 2-3 hours, adding 14-14.6 parts of triethylamine, raising the reaction temperature to 98-90 ℃ again, continuously reacting for 3 hours, cooling the obtained solid mixture, washing with dichloromethane, and drying to constant weight under vacuum at 90-100 ℃ to obtain an organic ligand; secondly, adjusting the pH value of a mixed solution of 180-200 parts by mass of 90% alcohol and 30-32 parts by mass of organic ligand to 8.5-9 by using 4.5-5wt% ammonia water solution, and stirring for 1-2 hours; uniformly mixing 6-8 parts of metal nano oxide, 2-4 parts of zinc borate and 75-85 parts of ethanol, then dripping into 30-32 parts of organic ligand and 180-200 parts of 90% alcohol mixed solution with the pH of 8.5-9 dropwise, stirring and refluxing for reaction for 5-6 hours, cooling, filtering and washing, and drying at 100 ℃ for 12-14 hours to obtain heat-conducting and heat-resistant powder; the metal nano oxide is one of zinc oxide and magnesium oxide.
Further, the mass ratio of the composite heat-conducting and heat-resistant powder to the adhesion promoter to the EVA premix in the first step is 24-27:7-9:88, the screw speed is 80-100 r/min, and the feeding speed is 8-10 r/min.
Further, the EVA premix in the second step is prepared from 68-75 parts by weight of ethylene-vinyl acetate copolymer, 15-20 parts by weight of chlorosulfonated grafted EVA and 0.9-1.2 parts by weight of dicumyl peroxide by stirring uniformly to obtain the EVA premix.
ZnO has better thermal stability, thermal conductivity and ultraviolet resistance, the thermal conductivity at room temperature is about 30W/(m.K), and pure zinc oxide is colorless and transparent. The high band gap brings the advantages of high breakdown voltage for Zn0, etc. Zinc borate has the advantages of no toxicity, good heat stability, whiteness, low tinting strength and good dispersibility, and can promote the high temperature resistance of the adhesive film. The heat-resistant flame-retardant modified polyethylene glycol terephthalate is blended with chlorosulfonated EVA and has good heat-resistant flame-retardant synergistic effect.
And adding an organic peroxide crosslinking agent, and when the EVA is heated to a certain temperature, decomposing the crosslinking agent to generate free radicals to trigger the combination between EVA molecules to form a three-dimensional network structure, so that the EVA adhesive layer is crosslinked and cured.
Further, the chlorosulfonated grafted EVA is prepared by the following steps: (1) Taking powdery EVA with the particle size of 560-600 mu m and the melt index of 2.2-3 g/10min, and putting the powdery EVA into a chlorination reaction kettle with a mixed solvent, wherein: the solid-liquid ratio of EVA to the mixed solvent is 1: 8-9; the mixed solvent is a mixed solvent of chloroform and carbon tetrachloride in a volume ratio of 1:1, and the mixed solvent contains 0.04-0.1% of dispersing agent, 0.003-0.005% of initiator and 0.05-0.1% of grafting monomer by weight of the mixed solvent; the chlorination reaction kettle is connected with a gas recovery device, the dispersing agent is talcum powder, the initiator is azodiisobutyronitrile, and the grafting monomer is maleic anhydride or methyl methacrylate; (2) grafting chlorination: heating the reaction kettle to above 70 ℃, introducing chlorine gas under the stirring condition, stirring for 1-3 hours at the temperature of 90-130 ℃, and controlling the pressure of the reaction kettle to be kept between 0.4-0.6 MPa and the chlorination degree to be 5-7%; (3) Continuously preheating the mixed gas to 45-50 ℃, introducing the preheated mixed gas into a reaction kettle, wherein the reaction pressure is 0.05-0.08 MPa, the reaction temperature is 70-80 ℃, and after reacting for 40-50 min, analyzing the chlorine and sulfur content, and when the chlorine content is 17-18%, the sulfur content is as follows: 0.5% -1%, discharging the materials out of the reaction kettle, washing and drying the solid materials obtained by solid-liquid separation to obtain chlorosulfonated grafted EVA, wherein the sulfonyl groups occupy a smaller proportion in the product, and chlorine atoms are main substituent groups, so that the control of the reaction end point can be realized simply according to the chlorination process of polyethylene, and the reaction end point is carried out according to the chlorine content of the system; the mixed gas consists of chlorine and sulfur dioxide, wherein the volume ratio of the chlorine to the sulfur dioxide is 1:0.2-0.3, and the adding speed of the mixed gas is 5-8% of the total adding amount per 10min.
The chlorosulfonated grafted EVA polymer can be used as a synergist of magnesium borate or zinc borate, so that the heat resistance is improved, and the EVA dispersion effect is achieved; in addition, chlorosulfonated grafting is taken as a relatively effective modification method, grafting can be carried out while chlorination is carried out, chlorosulfonation and grafting modification are combined into a whole, and the modification process is greatly simplified.
The chemical structure of chlorosulfonated grafted EVA is nearly saturated, and has better oxygen resistance, weather resistance, heat resistance and flame resistance, especially good heat resistance, the continuous service temperature of EVA film is improved, certain flame resistance is improved, and the antioxidant anti-aging agent can be even selected without adding and can be mixed with EVA for use.
The invention has the beneficial effects that:
the EVA film of the laminated glass on the market at present has good heat insulation performance and is not suitable for electric heating laminated glass, the chemical structure of chlorosulfonated grafted EVA is nearly saturated, has good chemical stability, particularly ozone and oxygen resistance, good heat resistance and fatigue resistance, and the grafted heat-resistant group also improves the heat resistance, so that the heat resistance of the EVA film in the high heat generation of the electric heating laminated glass is improved, when the electric heating glass is paved with an electric heating wire with the diameter of less than 0.01 mm, the electric heating glass is electrified, icing and fogging can be prevented, the sight line is not influenced, the good heat transfer and heat resistance are realized, the high anastomosis between glass layers is required, the optical effect of the glass is not influenced, the object is not deformed when seen, the heat conduction effect is realized in the long-term electric heating process, the original electric heating energy consumption is reduced, and the service life of the electric heating laminated glass in the long-term heat environment is prolonged. In the practical process, when the filling amount of the pure heat-conducting oxide reaches a certain degree, the method has the advantages that the cost is high, gaps are easy to form among inorganic oxide particles, meanwhile, damage and agglomeration are easy to occur, the heat resistance is further increased, the transparency of an EVA adhesive film is also affected by the overlarge filling amount, and the heat-conducting effect is not obviously improved. And because zinc oxide has high surface energy and a large number of hydroxyl groups on the surface, the zinc oxide is easy to aggregate into clusters, and the heat conduction performance is affected. By means of hybridization of triazine organic ligands and inorganic oxides, interfacial tension of the inorganic oxides is reduced, on one hand, the heat conduction network paths are further improved, however, the hybridized material presents a sphere similar to a microstructure, and dispersibility is greatly improved. The condensation reaction consumes surface hydroxyl groups through organic hybridization, thereby reducing the surface energy of the nano metal oxide. The organic modification layer is covered on the surface of the nano zinc oxide to generate larger steric hindrance, so that aggregation of particles is hindered, bonding effect among macromolecular chains of a matrix is enhanced, interaction among the macromolecular chains is remarkably enhanced, free volume of the macromolecular chains is reduced, and heat conduction capacity of the macromolecular chains of the matrix is enhanced. And through strengthening the interface bonding effect between EVA molecular chain and the filler, space three-dimensional network structure is easier to conduct heat, on the other hand, the oxazine-containing organic ligand group can improve the heat resistance and flame retardance of the composite heat conducting powder, plays a role in heat resistance and fire prevention, and provides higher reliability and safety for the use of the electric heating heat conducting glass.
Compared with the prior art, the invention has the following advantages:
the conventional EVA film which is not modified is general in the market, is soft, has hot melt adhesion, low in melting temperature, good in melt fluidity and heat-insulating, but is poor in heat resistance, is difficult to apply to electric heating laminated glass, is easy to extend and low in elasticity, is low in cohesive strength and poor in creep resistance, is easy to generate wafer fracture caused by expansion and contraction, causes bonding delamination, is poor in heat conduction effect, is not heat-resistant, and cannot be used for a long time.
The invention can greatly improve the heat conductivity coefficient, adopts organic ligand-metal oxide such as zinc oxide and magnesium oxide, is easy to contact with each other between particles, and is easier to form a heat conduction path in EVA. The EVA adhesive film filled with the heat-conducting heat-resistant powder has higher heat stability than the common EVA adhesive film, and the composite heat-conducting heat-resistant powder net chain plays a part of heat shielding effect on the EVA substrate, so that the heat decomposition rate of EVA is relieved, the heat stability of the EVA adhesive film is improved, the blended chlorosulfonated grafted EVA has excellent heat resistance, plays a role in anti-reflection, has heat-resistant and fireproof effects, provides higher reliability and safety, meets the heat-transfer and heat-resistant requirements of electric heating glass, has good light transmittance, has good shock resistance, and can not condense frost on the surface of the glass when being charged and heated, and can be used as a heat-conducting heat-resistant electric heating laminated glass adhesive for transporting airplanes, high-speed trains, ships and vessels, windshields of sports automobiles, display windows, show windows, building doors and windows in severe cold areas, knee-viewing towers and outdoor display screens.
Drawings
Fig. 1 is a thermal weight loss curve of EVA film of example 1, example 2, and comparative example 1.
Detailed Description
Example 1
Firstly, chlorosulfonated grafted EVA: (1) LOTTE VS440 powdery EVA with the average particle size of 600 mu m and the melt index of 2.2g/10min is taken and put into a chlorination reaction kettle added with mixed solvent, wherein: the solid-liquid ratio of EVA to the mixed solvent is 1:9, a step of performing the process; the mixed solvent is a mixed solvent of chloroform and carbon tetrachloride in a volume ratio of 1:1, and the mixed solvent contains 0.1 percent of dispersing agent, 0.005 percent of initiator and 0.1 percent of grafting monomer maleic anhydride by weight of the mixed solvent; the chlorination reaction kettle is connected with a gas recovery device, the dispersing agent is talcum powder, the initiator is azodiisobutyronitrile, (2) grafting chlorination: heating the reaction kettle to above 70 ℃, introducing chlorine gas under stirring, stirring for 3 hours at 130 ℃, controlling the pressure of the reaction kettle to be kept at 0.6MPa, and controlling the chlorination degree to be 7%; (3) Continuously preheating the mixed gas to 50 ℃, introducing the mixed gas into a reaction kettle, wherein the reaction pressure is 0.08MPa, the reaction temperature is 80 ℃, and after reacting for 40min, analyzing the chlorine and sulfur content, and when the chlorine content is 18%, the sulfur content is as follows: when the content of the chlorine and the sulfur dioxide is 1%, discharging the materials out of the reaction kettle, washing and drying the solid materials obtained through solid-liquid separation to obtain chlorosulfonated grafted EVA, wherein the mixed gas consists of chlorine and sulfur dioxide, the volume ratio of the chlorine to the sulfur dioxide is 1:0.3, and the adding speed of the mixed gas is 8% of the total adding amount per 10min.
The water absorption bottle is used for absorbing HCl gas emitted in the reaction process, and the principle is that the solubility of the HCl gas in water is extremely high and the HCl gas is easily absorbed by water; excess Cl which does not participate in the reaction during the reaction 2 After passing through a distilled water absorption bottle from the outlet of the reaction bottle, the part which is not absorbed is neutralized in a sodium hydroxide alkali solution bottle.
Secondly, preparing composite heat-conducting and heat-resistant powder: adding a new material including 32 parts of CG-560 gamma-aminopropyl triethoxysilane from Chen-Guanzhong into a reaction kettle equipped with a mechanical stirrer, then dropwise adding a mixture of 20 parts of dimethylacetamide, 27 parts of trichlorocyanuric acid and 14 parts of triethylamine into the reaction kettle under stirring at 800rpm in an external ice-water bath, after 3 hours, raising the reaction temperature to 50 ℃, dropwise adding a mixed solution of 19.2 parts of ethylenediamine and 10 parts of dimethylacetamide into the reaction kettle for 30 minutes, after 2 hours, dropwise adding 14 parts of triethylamine, raising the reaction temperature to 98 ℃ again for 3 hours, thereafter cooling and pouring the solid mixture into 45 parts of dimethylacetamide, filtering the precipitate and washing with dichloromethane, and drying under vacuum at 100 ℃ to constant weight to obtain an organic ligand; uniformly mixing 6 parts of nano zinc oxide, 2 parts of zinc borate and 75 parts of ethanol, then dripping the mixture into a mixed solution of 30 parts of organic ligand and 180 parts of 90% alcohol with the pH of 8.5 dropwise, stirring and refluxing at 600rpm for reaction for 5 hours, cooling, filtering and washing, and drying at 100 ℃ for 12 hours to obtain heat-conducting and heat-resistant powder; anhui contains four-needle nano zinc oxide whisker of mountain brocade zinc oxide factory with diameter of 0.8 μm, length of 3 μm, zinc borate with diameter of 0.1nm and length-diameter ratio of 30;
secondly, preparing EVA premix: 68 parts of COSMOPLENE TPC KA-40 brand ethylene-vinyl acetate copolymer containing 1.5% of dicumyl peroxide DCP by weight, 15 parts of chlorosulfonated grafted EVA and 0.9 part of dicumyl peroxide are uniformly stirred to obtain EVA premix. The tackifier is RGR-2 disproportionated rosin produced by Karaoke forest, and the weight ratio of the Wei TPR-803L terpene phenol resin is 1:1.
Finally, mixing the composite heat-conducting heat-resistant powder with the adhesion promoter and the EVA premix according to the mass ratio of 24:7:88, mixing the mixture with the adhesion promoter and the EVA premix at 50 ℃ for 15min in a high-speed mixer, drying the mixture at 45 ℃ for 1h, and winding the extruded casting film by a winding film unit, wherein the mass ratio of the composite heat-conducting heat-resistant powder to the adhesion promoter and the EVA premix is 24:7:88, and the extruder is provided with a screw speed of 80r/min and a feeding speed of 8 r/min.
The product is as follows: the thickness is 0.38mm, the heat conductivity coefficient is 1.83W/m.K, and the light transmittance is 90.5%; the degree of crosslinking is 93.0%; the peeling strength of the EVA film/glass is 71N/cm in normal state, 60N/cm after ultraviolet aging and 64N/cm after high-temperature high-humidity aging; a machine direction shrinkage of 1.1% and a transverse direction shrinkage of 0.5%; breakdown voltage strength 29.5KV/mm 3； Tensile strength 25.4MPa, elongation 430% and water absorptivity 0.01%; ultraviolet aging resistance (120 kW h/m) with a change in yellow index 3 ) 3.5; high temperature high humidity aging property (DH 1000) 3.6.
Example 2
Firstly, chlorosulfonated grafted EVA: (1) Powder EVAThe Polyolefin CompanyK3212 with a particle size of 560 μm and a melt index of 3 was taken and put into a chlorination reactor to which a mixed solvent was added, wherein: the solid-liquid ratio of EVA and the mixed solvent is 1:8; the mixed solvent is a mixed solvent of chloroform and carbon tetrachloride in a volume ratio of 1:1, and the mixed solvent contains 0.04 percent of dispersing agent, 0.003 percent of initiator and 0.05 percent of grafting monomer by weight of the mixed solvent; the chlorination reaction kettle is connected with a gas recovery device, the dispersing agent is talcum powder, the initiator is azodiisobutyronitrile, and the grafting monomer is methyl methacrylate; (2) grafting chlorination: heating the reaction kettle to 70 ℃, introducing chlorine gas under the stirring condition, stirring for 13 hours at the temperature of 90 ℃, and controlling the pressure of the reaction kettle to be kept at 0.4MPa and the chlorination degree to be 5%; (3) Continuously preheating the mixed gas to 45 ℃, introducing the mixed gas into a reaction kettle, wherein the reaction pressure is 0.05MPa, the reaction temperature is 70 ℃, and after reacting for 50min, analyzing the chlorine and sulfur content, and when the chlorine content is 17%, the sulfur content is as follows: and (3) when the content of the sulfur dioxide in the mixed gas is 0.5%, discharging the materials out of the reaction kettle, and washing and drying the solid materials obtained through solid-liquid separation to obtain chlorosulfonated grafted EVA, wherein the mixed gas consists of chlorine and sulfur dioxide, the volume ratio of the chlorine to the sulfur dioxide is 1:0.3, and the adding speed of the mixed gas is 8% of the total adding amount per 10min.
The water absorption bottle is used for absorbing HCl gas emitted in the reaction process, and the principle is that the solubility of the HCl gas in water is extremely high and the HCl gas is easily absorbed by water; excess Cl which does not participate in the reaction during the reaction 2 After passing through a distilled water absorption bottle from the outlet of the reaction bottle, the part which is not absorbed is neutralized in a sodium hydroxide alkali solution bottle.
Secondly, preparing composite heat-conducting and heat-resistant powder: adding 30 parts of Jiangxi Chen light New Material Co., ltd CG-560 gamma-aminopropyl triethoxysilane into a reaction kettle equipped with a mechanical stirrer, then stirring at 500rpm in an ice-water bath at 0 ℃, dropwise adding 15 parts of dimethylacetamide and 25 parts of trichlorocyanuric chloride, continuously stirring for reaction for 3 hours, raising the reaction temperature to 50 ℃, dropwise adding 19.2 parts of ethylenediamine and 12 parts of dimethylacetamide into the reaction kettle, reacting for 3 hours, adding 14.6 parts of triethylamine, raising the reaction temperature to 100 ℃ again, continuously reacting for 3 hours, washing distilled solid with dichloromethane after cooling, and drying to constant temperature under 100 ℃ vacuumAfter the weight is fixed, obtaining an organic ligand; uniformly mixing 8 parts of nano magnesium oxide, 4 parts of magnesium borate and 85 parts of ethanol, then dripping the mixture into a mixed solution with the pH of 9 of 32 parts of organic ligand and 200 parts of 90% alcohol by mass fraction, stirring and refluxing the mixture at 500rpm for reaction for 6 hours, cooling, filtering and washing the mixture, and drying the mixture at 100 ℃ for 14 hours to obtain heat-conducting and heat-resistant powder; the magnesium oxide is selected from the magnesium oxide whisker type I of Sichuan-Hamming technology development Co., ltd, the average diameter is 0.5 mu m, the length is 5 mu m, the heat conductivity is 254W/m.K, the magnesium borate is the magnesium borate whisker type II of Sichuan-Hamming technology, the length-diameter ratio is 30, and the bulk density is 0.6g/cm 3 ；
Secondly, preparing EVA premix: 75 parts of COSMEPLEETPCKA-40 ethylene-vinyl acetate copolymer, 20 parts of chlorosulfonated grafted EVA and 1.2 parts of dicumyl peroxide are uniformly stirred to obtain EVA premix. The tackifier is a mixture of a SUMITE RP-19900 thermoplastic phenolic resin and a Marsdenia tenacissima MR115 rosin in a mass ratio of 1:1.
And finally, mixing the composite heat-conducting and heat-resisting powder with the adhesion promoter and the EVA premix according to the mass ratio of 27:9:88, mixing the mixture with the adhesion promoter and the EVA premix at 60 ℃ for 20min in a high-speed mixer, drying the mixture at 50 ℃ for 2h, and winding the extruded casting film by a winding film unit, wherein the screw speed of the extruder is 100r/min, and the feeding speed is 10r/min.
The product is as follows: the thickness is 0.38mm, the heat conductivity coefficient is 1.97W/m.K, and the light transmittance is 90.1%; the degree of crosslinking is 93.4%; the peeling strength of the EVA film/glass is 75N/cm in normal state, 61N/cm after ultraviolet aging and 67N/cm after high-temperature high-humidity aging; a machine direction shrinkage of 0.9% and a transverse direction shrinkage of 0.4%; breakdown voltage strength 26.7KV/mm 3； Tensile strength 24.3MPa, elongation 435% and water absorptivity 0.012%; ultraviolet aging resistance (120 kW h/m) with a change in yellow index 3 ) 3.4; high temperature high humidity aging property (DH 1000) 3.8.
Comparative example 1
The extrusion process was the same as in example 1 using the neat EVA film of example.
The heat conductivity coefficient is 0.231W/mK.
The extrusion casting film coating processes of examples 1-2 and comparative example 1 are shown in table 1:
TABLE 1 extrusion casting film coating process parameters of EVA film production line of examples 1-2 and comparative example
Note that: crosslinking degree, peeling strength, shrinkage, 120mm, 25mm tensile strength and elongation at break, light transmittance, breakdown voltage strength with diameter of 50mm, yellow index change, temperature of 85-humidity of 85%, strength after continuous 1000h high temperature high humidity aging, irradiation of 250W/m 2 After ultraviolet aging at 85 ℃ and humidity of 60 percent (120 kW.h) 2 ) Reference is made to HG/T5377-2018 ethylene-vinyl acetate (EVA) adhesive films; thermal conductivity referring to astm d5470-2017 thermal conductive solid electrically insulating thin material thermal conductivity performance test method; wherein the room temperature is 25 ℃, the curing process is that in an astronomical YDS-1010 laminating machine, the air is pumped out at 142 ℃ for 6min, then the air is put into a curing oven to be cured for 10min under the condition of pressurizing and heat preservation at 142 ℃, and then the air is cooled to the room temperature. One chamber temperature 140 ℃, one chamber vacuumizing time 400s, one chamber laminating time 100s, cover opening inflating 30s, two chamber temperature 140 ℃, two chamber vacuumizing time 30s, two chamber laminating time 400s and cover opening inflating 30s; wherein the peeling speed is 100mm/min; high temperature and high humidity aging performance: shanghai forest frequency LRHS-101B-LH programmable constant temperature and humidity aging box; test conditions: the test piece with the three layers of glass/EVA/glass is used as a test piece with the temperature of 85 ℃ and the humidity of 85%, and is cooled to the room temperature after 1000 hours of continuous test, and the heating speed is 5 ℃/min by a Pyris1TGA thermal analyzer.
In conclusion, the preparation method of the heat-conducting and heat-resistant EVA film for laminated glass disclosed by the invention can improve the heat-conducting and heat-resistant performance of the laminated glass by blending and modifying the composite heat-conducting and heat-resistant powder and chlorosulfonated EVA, has the comprehensive performance higher than the industry standard, such as HG/T5377-2018, has heat-resistant and fireproof effects, provides higher reliability and safety, meets the heat-conducting and heat-resistant requirements of electric heating glass, has good light transmittance, has good shock resistance, and can not condense frost on the surface of the glass when being charged and heated, and can be used as heat-conducting and heat-resistant electric heating laminated glass adhesive for windshields of conveyors, high-speed trains and sports automobiles, ships display windows, shop windows, building doors and windows in severe cold areas, knee-wear windows and outdoor display screens, thereby improving the embarrassment that common EVA adhesive is difficult to be applied to electric heating laminated glass.
Claims (3)
1. The preparation method of the heat-conducting and heat-resistant EVA film for laminated glass is characterized by comprising the following steps of: mixing the composite heat-conducting and heat-resistant powder with an adhesion promoter and EVA premix in proportion in a high-speed mixer at 50-60 ℃ for 15-20 min, drying at 45-50 ℃ for 1-2 h, and winding the extruded cast film by a film winding unit to obtain the heat-conducting and heat-resistant composite heat-resistant powder;
adding 30-32 parts of gamma-aminopropyl triethoxysilane into a reaction kettle provided with a mechanical stirrer, stirring in an ice-water bath at 0 ℃, dropwise adding 15-20 parts of dimethylacetamide and 25-27 parts of trichlorocyanuric chloride, continuously stirring and reacting for 2.5-3 hours, raising the reaction temperature to 45-50 ℃, dropwise adding 19-19.2 parts of ethylenediamine and 10-12 parts of dimethylacetamide into the reaction kettle, reacting for 2-3 hours, adding 14-14.6 parts of triethylamine, raising the reaction temperature to 98-90 ℃ again, continuously reacting for 3 hours, cooling the obtained solid mixture, washing with dichloromethane, and drying to constant weight under vacuum at 90-100 ℃ to obtain the organic ligand; secondly, uniformly mixing 6-8 parts of metal nano oxide, 2-4 parts of borate and 75-85 parts of ethanol, then dripping into 30-32 parts of organic ligand and 180-200 parts of 90% alcohol mixed solution with the pH of 8.5-9 dropwise, stirring and refluxing for reaction for 5-6 hours, cooling, filtering and washing, and drying at 100 ℃ for 12-14 hours to obtain heat-conducting and heat-resistant powder; the metal nano oxide is zinc oxide or magnesium oxide, and the borate is zinc borate or magnesium borate;
the EVA premix is prepared from 68-75 parts by weight of ethylene-vinyl acetate copolymer, 15-20 parts by weight of chlorosulfonated grafted EVA and 0.4-0.7 part by weight of dicumyl peroxide by uniformly stirring to obtain an EVA premix;
the chlorosulfonated grafted EVA is prepared by the following steps: (1) Taking powdery EVA, and putting the EVA into a chlorination reaction kettle added with a mixed solvent of chloroform and carbon tetrachloride in a volume ratio of 1:1, wherein the solid-liquid ratio of the EVA to the mixed solvent is 1: 8-9; the mixed solvent contains 0.04-0.1% of talcum powder dispersing agent, 0.003-0.005% of AIBN initiator and 0.05-0.1% of grafting monomer by weight of the mixed solvent, wherein the grafting monomer is maleic anhydride or methyl methacrylate; (2) grafting chlorination: heating the reaction kettle to 70 ℃, introducing chlorine gas under stirring, stirring for 1-3 hours at the temperature of 90-130 ℃, and controlling the pressure of the reaction kettle to be 0.4-0.6 MPa and the chlorination degree to be 5-7%; (3) Continuously preheating the mixed gas to 25-70 ℃, and then introducing the preheated mixed gas into a reaction kettle, wherein the reaction pressure is 0.1-0.2 MPa, the reaction temperature is 70-80 ℃, the reaction time is 40-50 min, and when the chlorine content is 17-18%, the sulfur content is: and when 0.5-1%, discharging the materials, and performing solid-liquid separation, washing and drying to obtain chlorosulfonated grafted EVA, wherein the mixed gas consists of chlorine and sulfur dioxide, the volume ratio of the chlorine to the sulfur dioxide is 1:0.2-0.3, and the adding speed of the mixed gas is 5-8% of the total adding amount per 10min.
2. The method for preparing the heat-conducting and heat-resistant EVA film for laminated glass according to claim 1, wherein the tackifier is one or more of disproportionated rosin, terpene phenol resin, thermoplastic phenolic resin and maleic rosin.
3. The preparation method of the heat-conducting and heat-resistant EVA film for laminated glass, according to claim 1, wherein the mass ratio of the composite heat-conducting and heat-resistant powder to the adhesion promoter to the EVA premix is 24-27:7-9:88.
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