CN115926666A - Preparation method of heat-conducting and heat-resisting EVA (ethylene-vinyl acetate) film for laminated glass - Google Patents
Preparation method of heat-conducting and heat-resisting 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 heat-resistant EVA film of laminated glass, which belongs to the technical field of glass laminated adhesives, wherein the heat-conducting heat-resistant performance of the heat-conducting heat-resistant EVA film is improved through blending modification of composite heat-conducting heat-resistant powder and chlorosulfonated EVA, an organic triazine ligand hybridized heat-conducting magnesium oxide or zinc oxide maintains stability and promotes crosslinking, simultaneously, a heat-conducting network channel is perfected, agglomerated clusters are reduced, the interface bonding effect between a matrix molecular chain and a filler is enhanced, the heat-conducting heat-resistant EVA film has heat-resistant and fireproof effects, higher reliability and safety are provided, the heat-conducting heat-resistant requirements of electric heating glass are met, the light transmittance is good, the impact resistance is good, and when charging and heating are carried out, frost cannot be condensed on the surface of the glass, and the heat-conducting heat-resistant electric heating laminated glass adhesive can be used as windshields of transport planes, high-speed trains, naval vessels and sports cars, display windows, building doors and windows in severe cold regions, knee-looking tower windows and outdoor display screens.
Description
Technical Field
The invention belongs to the technical field of glass interlayer adhesive, and particularly relates to a preparation method of a heat-conducting and heat-resistant EVA (ethylene vinyl acetate) adhesive sheet for laminated glass.
Background
The obvious heat insulation performance of the laminated glass well caters to the common practice of adopting a glass curtain wall in a large area in modern buildings. In the past, people had to bear the love of being limited to the poor thermal insulation performance of traditional glass. The problem of good heat insulation performance of laminated glass made of the plastic intermediate film is overcome. The laminated glass has greatly improved heat transfer in the convection heat transfer portion compared to the performance of a single sheet of glass, and the convection heat transfer is reduced by the low thermal conductivity. The sun-screening and heat-insulating functions of laminated glass have been known. The electrically heated glass is a glass product capable of heating after being electrified, and is prepared by depositing a metal heat-conducting film on laminated glass or arranging a resistance wire in an intermediate layer material to ensure that the glass product has electric heating performance, and a temperature regulator is generally used for controlling the heating temperature. The glass can be electrified and heated to remove ice and frost and keep the glass in the optimal working state; for example, electrically heated glass is required for the cab windows of the CRH380AL motor car. For example, CN214164702U, etc., the car also uses electric heating laminated glass, and the cab window of the high-speed railway train uses electric heating laminated glass in which heating wires with a diameter less than 0.01 mm are laid, and the glass is heated by electrifying, so as to prevent icing, so as to avoid affecting the sight. CN201895553U discloses a double-layer black-edge local silver wire electric heating laminated glass, and for another example, chinese patent CN201491304U discloses a sandwiched wire heating laminated glass with a temperature control switch, which is arranged on PVB, wherein two ends of a plurality of heating wires are connected with two buses, and then are connected with the buses through two electrode wires. Chinese patent CN104540256A discloses a method for preparing electric heating laminated glass, and because the adhesive film of the laminated glass has good heat-insulating property, actually the defrosting and defogging effects are not good, it is necessary to increase the heating temperature and heating time, after long-time heating and higher temperature use, the polymer adhesive film has poor heat-radiating property, and is subjected to long-time heat aging, whether the phenomena of shrinking, degumming, yellowing and hardening exist at the edges of the intermediate film and the glass, and the transparency is reduced due to long-term action, thus seriously affecting the use. The heat dissipation problem is also urgently needed to be solved due to the high temperature in the PV assembly for a long time. In recent years, a plurality of novel membrane materials are developed at home and abroad, such as EN laminated films, which are high-viscosity thin film materials processed by special equipment by taking ethylene and vinyl acetate copolymers as main raw materials, and are also called EVA laminated glass films. The EN film for the outdoor building has ultrahigh transparency, good adhesion, weather resistance and impact resistance. However, the heat resistance of EVA is poor, and the improvement of the heat conductivity and the heat resistance is a necessary prerequisite for the application of the EVA clamping sheet as the electric heating laminated glass. Those skilled in the art are keenly to develop a method for preparing 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 this, 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-resisting EVA (ethylene vinyl acetate) film for laminated glass comprises the following steps: firstly, mixing the composite heat-conducting heat-resisting powder with a tackifier and an EVA premix according to a set proportion in a high-speed mixer at 50-60 ℃ for 15-20min, drying at 45-50 ℃ for 1-2h, extruding, casting, laminating, and winding by a film winding machine set to obtain the heat-conducting heat-resisting composite heat-conducting heat-resisting powder.
Further, the tackifier is one or more of disproportionated rosin, terpene phenol resin, thermoplastic phenolic resin and maleic rosin.
The reaction is as follows:
further, adding 30-32 parts by weight of gamma-aminopropyltriethoxysilane 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 trichloromelamine, continuously stirring for reaction 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, then adding 14-14.6 parts of triethylamine, raising the reaction temperature to 98-90 ℃ for continuous reaction for 3 hours, cooling the obtained solid mixture, washing with dichloromethane, and drying at 90-100 ℃ under vacuum to constant weight to obtain an organic ligand; secondly, adjusting the pH 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 an ammonia water solution with the mass percent of 4.5-5 wt%, 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, dropwise adding the mixture into a mixed solution of 30-32 parts of organic ligand and 180-200 parts of 90% by mass ethanol, wherein the pH value is 8.5-9, stirring, refluxing for 5-6 hours, cooling, filtering, washing, drying at 100 ℃ for 12-14h, and obtaining heat-conducting and heat-resistant powder; the metal nano oxide is one of zinc oxide and magnesium oxide.
Further, the mass ratio of the first composite heat-conducting heat-resisting powder to the tackifier to the EVA premix is 24-27: 7-9: 88, the screw rotation speed is 80-100r/min, and the feeding speed is 8-10r/min.
Furthermore, the EVA premix of the second step is prepared from 68 to 75 parts by weight of an ethylene-vinyl acetate copolymer, 15 to 20 parts by weight of chlorosulfonated grafted EVA and 0.9 to 1.2 parts by weight of dicumyl peroxide, and is uniformly stirred 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 energy band gap brings high breakdown voltage for Zn0 and the like. The zinc borate has the advantages of no toxicity, good thermal stability, white color, low tinting strength and good dispersibility, and can promote the high temperature resistance of the adhesive film. The flame retardant is blended with chlorosulfonated EVA and has good heat-resistant flame-retardant synergistic effect.
Adding organic peroxide cross-linking agent, when EVA is heated to a certain temperature, the cross-linking agent is decomposed to generate free radicals, and the combination between EVA molecules is initiated to form a three-dimensional network structure, so that the EVA adhesive layer is cross-linked and cured.
Further, the chlorosulfonated grafted EVA is prepared by the following steps: (1) Taking powdery EVA with the particle size of 560 to 600 mu m and the melt index of 2.2 to 3g/10min, and putting the powdery EVA into a chlorination reaction kettle added with a mixed solvent, wherein: the solid-liquid ratio of the EVA to the mixed solvent is 1:8 to 9; the mixed solvent is a mixed solvent of trichloromethane and carbon tetrachloride in a volume ratio of 1: 1, and the mixed solvent contains 0.04 to 0.1 percent of dispersant, 0.003 to 0.005 percent of initiator and 0.05 to 0.1 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 maleic anhydride or methyl methacrylate; (2) graft chlorination: heating the reaction kettle to more than 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 mixed gas into a reaction kettle, reacting at 70-80 ℃ under the pressure of 0.05MPa to 0.08MPa and at the temperature of 0-80 ℃, and after reacting for 40-50min, analyzing the contents of chlorine and sulfur, wherein when the chlorine content is 17-18%, the sulfur content: when the content is 0.5-1%, discharging the material out of the reaction kettle, washing and drying the solid material obtained by solid-liquid separation to obtain chlorosulfonated grafted EVA, wherein the content of sulfonyl groups in the product is small, and chlorine atoms are main substituent groups, so that the control of a reaction end point can be simply realized according to the chlorination process of polyethylene and is carried out according to the chlorine content of a system; wherein the mixed gas consists of chlorine and sulfur dioxide, the volume ratio of the chlorine to the sulfur dioxide is 1.2 to 0.3, and the adding speed of the mixed gas is 5 to 8 percent of the total adding amount per 10min.
The chlorosulfonated grafted EVA polymer can be used as a synergist of magnesium borate or zinc borate, improves heat resistance and plays a role in dispersing EVA; in addition, chlorosulfonation grafting is used as a relatively effective modification method, grafting can be carried out while chlorination is carried out, chlorosulfonation and grafting modification are combined into one, and the modification process is greatly simplified.
The chlorosulfonated grafted EVA has a nearly saturated chemical structure, has good oxygen resistance, weather resistance, heat resistance and flame retardancy, particularly good heat resistance, improves the continuous use temperature of the EVA film, improves certain flame resistance, and can be blended with EVA for use even without adding an antioxidant anti-aging agent.
The invention has the beneficial effects that:
the EVA film of the laminated glass on the market at present has good heat-insulating property generally, and is not suitable for the electric heating laminated glass, the invention is through blending the modified chlorosulfonated EVA, the chemical structure of chlorosulfonated grafted EVA is nearly saturated and has good chemical stability, especially ozone and oxygen resistance, good heat resistance, and fatigue resistance, the heat resistance has also been improved to graft the heat-resisting group, and then has improved the tolerance ability of EVA film in the high heating of the electric heating laminated glass, lay the heating wire with diameter less than 0.01 millimeter in the electric heating glass, can prevent icing and fogging, does not influence the sight, and have better heat transfer and heat-resisting property, must keep high identical between the glass layer, does not influence the optical effect of the glass, see things and does not deform, in the long-term electric heating process, have heat conduction effect, reduce the energy consumption of the original electric heating, improve its service life under the long-term thermal environment at the same time. In the practical process, when the filling amount of the pure heat-conducting oxide reaches a certain degree, the cost is high, gaps are easily formed among inorganic oxide particles, damage and agglomeration phenomena are very easily caused, the thermal resistance is further increased, the transparency of the EVA adhesive film is also influenced by overlarge filling amount, and the improvement of the heat-conducting effect is not obvious. And because the surface energy of the zinc oxide is high, a large number of hydroxyl groups are arranged on the surface, and the zinc oxide is easy to gather into clusters, thereby influencing the heat-conducting property. Through hybridization of the triazine organic ligand and the inorganic oxide, the interfacial tension of the inorganic oxide is reduced, on one hand, a heat conduction network path is further improved, however, the hybrid material presents a spherical shape similar to a microstructure, and the dispersibility is greatly improved. The surface hydroxyl groups are consumed by the condensation reaction through organic hybridization, so that the surface energy of the nano metal oxide is reduced. The organic modification layer covers the surface of the nano zinc oxide to generate larger steric hindrance, so that the aggregation of particles is hindered, the bonding effect among the macromolecular chains of the matrix is enhanced, the interaction among the macromolecular chains is obviously enhanced, the free volume of the macromolecular chains is reduced, and the heat conduction capability of the macromolecular chains of the matrix is enhanced. And the interface bonding effect between the EVA molecular chain and the filler is enhanced, the spatial three-dimensional network structure is easier to conduct heat, and on the other hand, the organic ligand group containing the oxazine can improve the heat resistance and the fire resistance 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 general unmodified EVA film on the market is soft, has hot-melt adhesiveness, low melting temperature, good melting fluidity and heat insulation, but has poor heat resistance, is difficult to apply to electric heating laminated glass, is easy to extend and low in elasticity, low in cohesive strength and poor in creep resistance, is easy to generate thermal expansion and cold contraction to cause chip cracking and bond delamination, has poor heat conduction effect, is not heat-resistant, and cannot be used for a long time.
The invention can greatly improve the heat conductivity coefficient, and the organic ligand-metal oxide such as zinc oxide and magnesium oxide is adopted, so that the particles are easy to contact with each other, and a heat conduction path is easier to form in the EVA. The EVA adhesive film filled with the heat-conducting heat-resistant powder has higher heat stability than a common EVA adhesive film, and the composite heat-conducting heat-resistant powder net chain plays a part of heat shielding effect on an EVA matrix, so that the thermal decomposition rate of EVA is relieved, the heat stability of the EVA is improved, the blended chlorosulfonated grafted EVA has excellent heat resistance, plays a role in increasing the permeability, 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 and good impact resistance, can not condense frost on the surface of glass when charged and heated, and can be used as heat-conducting heat-resistant electrically-heated laminated glass adhesive for windshields of transportation airplanes, high-speed trains, naval vessels, sports cars, display windows, shop windows, building doors and windows in cold regions, knee-looking tower windows and outdoor display screens.
Drawings
FIG. 1 shows thermogravimetric curves of EVA sheets of examples 1 and 2 and comparative example 1.
Detailed Description
Example 1
Firstly, chlorosulfonation grafting EVA: (1) Taking LOTTE VS440 powdery EVA with the average grain diameter of 600 mu m and the melt index of 2.2g/10min, and putting the EVA into a chlorination reaction kettle added with a mixed solvent, wherein: the solid-liquid ratio of the EVA to the mixed solvent is 1:9; the mixed solvent is a mixed solvent of trichloromethane and carbon tetrachloride in a volume ratio of 1: 1, and the mixed solvent contains 0.1 percent of dispersant, 0.005 percent of initiator and 0.1 percent of grafting monomer maleic anhydride based on the 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 azobisisobutyronitrile, (2) grafting chlorination: heating the reaction kettle to above 70 ℃, introducing chlorine gas under the stirring condition, stirring for 3 hours at the temperature of 130 ℃, and controlling the pressure of the reaction kettle to be kept at 0.6MPa and the chlorination degree to be 7%; (3) Continuously preheating the mixed gas to 50 ℃, introducing the mixed gas into a reaction kettle, reacting for 40min at the reaction temperature of 80 ℃ and under the reaction pressure of 0.08MPa, and analyzing the contents of chlorine and sulfur, wherein when the chlorine content is 18 percent, the sulfur content is as follows: when the content of the chlorine gas in the mixed gas is1 percent, the mixed gas is discharged out of the reaction kettle, the solid material obtained through solid-liquid separation is washed and dried to obtain chlorosulfonated grafted EVA, wherein the mixed gas consists of chlorine gas and sulfur dioxide, the volume ratio of the chlorine gas to the sulfur dioxide is 1.3, and the adding speed of the mixed gas is 8 percent of the total adding amount per 10min.
The water absorption bottle is used for absorbing HCl gas released in the reaction process, and the principle is that the HCl gas has extremely high solubility in water and is easily absorbed by water; excessive Cl not participating in the reaction process 2 And after passing through a distilled water absorption bottle from the outlet of the reaction bottle, the unabsorbed part enters a sodium hydroxide alkaline solution bottle again to be neutralized.
Secondly, preparing the composite heat-conducting heat-resisting powder: adding 32 parts of CG-560 gamma-aminopropyltriethoxysilane into a reaction kettle equipped with a mechanical stirrer, then dropwise adding a mixture of 20 parts of dimethylacetamide, 27 parts of trichloromelamine and 14 parts of triethylamine into the reaction kettle while stirring at 800rpm in an external ice-water bath for 3 hours, then 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, 2 hours later, dropwise adding 14 parts of triethylamine, raising the reaction temperature to 98 ℃ again and reacting for 3 hours, thereafter, cooling and pouring the solid mixture into 45 parts of dimethylacetamide, then filtering and washing the precipitate with dichloromethane, and drying under a vacuum of 100 ℃ to a 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, dropwise adding the mixture into a mixed solution of 30 parts of organic ligand and 180 parts of 90% alcohol by mass and with the pH value of 8.5, stirring at 600rpm, carrying out reflux reaction for 5 hours, cooling, filtering, washing, and drying at 100 ℃ for 12 hours to obtain heat-conducting heat-resistant powder; the diameter of the four-needle nano zinc oxide whisker in the Shanjin Hua zinc oxide factory in Anhui province is 0.8 mu m, the length of the four-needle nano zinc oxide whisker is 3 mu m, the diameter of zinc borate is 0.1nm, and the length-diameter ratio of the zinc borate is 30;
secondly, preparing EVA premix: 68 parts of COSMOPLENE TPC KA-40 grade ethylene-vinyl acetate copolymer containing 1.5% of dicumyl peroxide DCP in parts by weight, 15 parts of chlorosulfonated grafted EVA and 0.9 part of dicumyl peroxide by weight are uniformly stirred to obtain the EVA premix. The tackifier is a mixture of RGR-2 disproportionated rosin produced in cany parasol forests and Velcro-803L terpene phenol resin in a mass ratio of 1: 1.
And finally, mixing the composite heat-conducting heat-resisting powder with the tackifier and the EVA premix at a mass ratio of 24: 7: 88 in a high-speed mixer at 50 ℃ for 15min, drying at 45 ℃ for 1h, extruding, casting, laminating, winding by a winding film machine set, wherein the mass ratio of the composite heat-conducting heat-resisting powder to the tackifier and the EVA premix is 24: 7: 88, the screw rotating speed of an extruder is 80r/min, and the feeding speed is 8 r/min.
In the product: the thickness is 0.38mm, the heat conductivity coefficient is 1.83W/m.K, and the light transmittance is 90.5 percent; the degree of crosslinking is 93.0%; the peel strength of the EVA film/glass is 71N/cm at normal state, 60N/cm after ultraviolet aging and 64N/cm after high-temperature high-humidity aging; longitudinal shrinkage of 1.1% and transverse shrinkage of 0.5%; breakdown voltage strength 29.5KV/mm 3； Tensile strength is 25.4MPa, elongation is 430 percent, and water absorptivity is 0.01 percent; yellow index change ultraviolet aging resistance (120 kW.h/m) 3 ) 3.5; high temperature and high humidity aging Performance (DH 1000) 3.6.
Example 2
Firstly, chlorosulfonation grafting EVA: (1) Taking powdery EVAThe Polyolefin company K3212 with the grain diameter of 560 mu m and the melt index of 3, and putting the powdery EVAThe Polyolefin company K3212 into a chlorination reaction kettle added with a mixed solvent, wherein: the solid-liquid ratio of the EVA to the mixed solvent is 1: 8; the mixed solvent is a mixed solvent of trichloromethane and carbon tetrachloride in a volume ratio of 1: 1, and the mixed solvent contains 0.04 percent of dispersant, 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) graft chlorination: heating the reaction kettle to 70 ℃, introducing chlorine gas under the stirring condition, stirring the mixture for 13 hours at the temperature of 90 ℃, and controlling the pressure of the reaction kettle to be 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, reacting for 50min at the reaction temperature of 70 ℃ and under the reaction pressure of 0.05MPa, and analyzing the contents of chlorine and sulfur, wherein when the chlorine content is 17%, the sulfur content is: when the content of the chlorine is 0.5 percent, 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 1.3, and the adding speed of the mixed gas is 8 percent of the total adding amount per 10min.
The HCl gas released in the reaction process is absorbed by a water absorption bottle, and the principle is that the HCl gas has extremely high solubility in water and is very easy to absorb by water; excessive Cl not participating in the reaction process 2 And after passing through a distilled water absorption bottle from the outlet of the reaction bottle, the unabsorbed part enters a sodium hydroxide alkaline solution bottle again to be neutralized.
Secondly, preparing the composite heat-conducting heat-resisting powder: adding 30 parts of CG-560 gamma-aminopropyltriethoxysilane from Jiangxi Chenguang New Material Co., ltd into a reaction kettle equipped with a mechanical stirrer, stirring at 500rpm in an ice water bath at 0 ℃, dropwise adding 15 parts of dimethylacetamide and 25 parts of trichloromelamine, 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, and reactingAfter 3 hours, adding 14.6 parts of triethylamine, raising the reaction temperature to 100 ℃ again, continuing to react for 3 hours, cooling the distilled solid, washing the solid with dichloromethane, and drying the solid at 100 ℃ in vacuum to constant weight to obtain an organic ligand; uniformly mixing 8 parts of nano magnesium oxide, 4 parts of magnesium borate and 85 parts of ethanol, dropwise adding the mixture into a mixed solution of 32 parts of organic ligand and 200 parts of 90% alcohol by mass and with the pH value of 9, stirring at 500rpm, carrying out reflux reaction for 6 hours, cooling, filtering, washing, and drying at 100 ℃ for 14 hours to obtain heat-conducting heat-resistant powder; selecting magnesium oxide, wherein the average diameter of I-type magnesium oxide whisker of Sichuan Haoming science and technology development Limited is 0.5 mu m, the length is 5 mu m, the thermal conductivity is 254W/m.K, the magnesium borate is II-type magnesium borate whisker of Sichuan Haoming science and technology, the length-diameter ratio is 30, and the bulk density is 0.6g/cm 3 ；
Secondly, preparing EVA premix: the EVA premix is prepared by uniformly stirring 75 parts by weight of COSMOPLENETPCKA-40 ethylene-vinyl acetate copolymer, 20 parts by weight of chlorosulfonated grafted EVA and 1.2 parts by weight of dicumyl peroxide. The tackifier is a mixture of Sumileite RP-19900 thermoplastic phenolic resin and MR115 maleated rosin produced by Xanthium chinense forest in a mass ratio of 1: 1.
And finally, mixing the composite heat-conducting heat-resisting powder with the tackifier and the EVA premix at a high-speed mixer for 20min at 60 ℃ and drying for 2h at 50 ℃ according to the mass ratio of the composite heat-conducting heat-resisting powder to the tackifier and the EVA premix of 27: 9: 88, and then rolling the extruded casting laminated film by a film winding machine set, wherein the rotating speed of a screw 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 percent; the degree of crosslinking was 93.4%; the peel strength of the EVA film/glass is 75N/cm at normal state, 61N/cm after ultraviolet aging and 67N/cm after high-temperature high-humidity aging; longitudinal shrinkage of 0.9% and transverse shrinkage of 0.4%; breakdown voltage strength of 26.7KV/mm 3； Tensile strength of 24.3MPa, elongation of 435 percent and water absorption rate of 0.012 percent; yellow index change ultraviolet aging resistance (120 kW.h/m) 3 ) 3.4; high temperature and high humidity aging Performance (DH 1000) 3.8.
Comparative example 1
The extrusion process was the same as in example 1, using the pure EVA film of example 1.
The thermal conductivity was 0.231W/m.K.
The extrusion casting lamination processes of examples 1 to 2 and comparative example 1 are shown in table 1:
TABLE 1 EVA film production line extrusion, casting and laminating process parameters of examples 1 to 2 and comparative examples
Note: crosslinking degree, peeling strength, shrinkage, tensile strength and elongation at break of 120mm and 25mm, light transmittance, breakdown voltage strength of 50mm in diameter, change of yellow index, temperature of 85-85% humidity, strength after continuous 1000h high-temperature high-humidity aging, and irradiation of 250W/m 2 And an after-UV aged strength (120 kW. H) of 85 ℃ humidity 60% 2 ) Reference is made to HG/T5377-2018 ethylene-vinyl acetate (EVA) adhesive film; the heat conductivity refers to a method for testing the heat conduction performance of a heat conduction solid electric insulation thin material in ASTM D5470-2017; wherein the room temperature is 25 ℃, the curing process is in an aerospace YDS-1010 laminator, the temperature is 142 ℃ and is evacuated for 6min, then the laminate is placed in a curing furnace to be pressurized and insulated at the temperature of 142 ℃ for curing for 10min, and then the laminate is cooled to the room temperature. The first cavity temperature is 140 ℃, the first cavity vacuumizing time is 400s, the first cavity laminating time is 100s, the cover opening air charging time is 30s, the second cavity temperature is 140 ℃, the second cavity vacuumizing time is 30s, the second cavity laminating time is 400s, and the cover opening air charging time is 30s; wherein the peeling speed is 100mm/min; high temperature, high humidity and aging performance: shanghai forest frequency LRHS-101B-LH programmable constant temperature and humidity aging box; the test conditions are as follows: the temperature and the humidity of a test piece formed by laminating the three layers of glass/EVA/glass are 85 ℃, the test piece is continuously tested for 1000 hours and then cooled to the room temperature, and a Pyris1TGA thermal analyzer is used for heating at the speed of 5 ℃/min.
In conclusion, the heat-conducting heat-resistant EVA film for laminated glass disclosed by the invention can improve the heat-conducting heat-resistant performance of the laminated glass by blending modification of the composite heat-conducting heat-resistant powder and chlorosulfonated EVA, the comprehensive performance is higher than the industrial standard, such as HG/T5377-2018, the heat-conducting heat-resistant EVA film has heat-resistant and fireproof effects, higher reliability and safety are provided, the heat-conducting heat-resistant requirement of electric heating glass is met, the light transmittance is good, the impact resistance is good, frost is not condensed on the surface of the glass during charging and heating, the laminated glass can be used as heat-conducting heat-resistant electric heating laminated glass adhesive for windshields of transporters, high-speed trains and sports cars, ship display windows, show windows, building doors and windows in severe cold regions, knee-view tower windows and outdoor display screens, and the embarrassment that the common EVA adhesive is difficult to be applied to the electric heating laminated glass is improved.
Claims (6)
1. The preparation method of the heat-conducting and heat-resisting EVA film for the laminated glass is characterized by comprising the following steps of: mixing the composite heat-conducting heat-resisting powder with the tackifier and the EVA premix according to a ratio in a high-speed mixer at 50-60 ℃ for 15-20min, drying at 45-50 ℃ for 1-2h, extruding, casting, laminating, and winding by a winding film machine set to obtain the heat-conducting heat-resisting composite film.
2. The method for preparing the heat-conducting and heat-resisting EVA film of the 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 laminated glass heat-conducting heat-resisting EVA film according to claim 1, characterized in that 30 to 32 parts by weight of gamma-aminopropyltriethoxysilane are added into a reaction kettle provided with a mechanical stirrer, then the mixture is stirred in an ice water bath at 0 ℃, 15 to 20 parts of dimethylacetamide and 25 to 27 parts of trichloromelamine are dropwise added, the mixture is continuously stirred and reacted for 2.5 to 3 hours, the reaction temperature is increased to 45 to 50 ℃, then 19 to 19.2 parts of ethylenediamine and 10 to 12 parts of dimethylacetamide are dropwise added into the reaction kettle, the mixture is reacted for 2 to 3 hours, then 14 to 14.6 parts of triethylamine is added, the reaction temperature is increased to 98 to 90 ℃ again, the reaction is continued for 3 hours, the obtained solid mixture is cooled, washed with dichloromethane, and dried under vacuum at 90 to 100 ℃ to a constant weight to obtain the organic ligand; secondly, uniformly mixing 6 to 8 parts of metal nano oxide, 2 to 4 parts of borate and 75 to 85 parts of ethanol, dropwise adding the mixture into a mixed solution of 30 to 32 parts of organic ligand and 180 to 200 parts of 90% ethanol by mass, wherein the pH value is 8.5 to 9, stirring, refluxing, reacting for 5 to 6 hours, cooling, filtering, washing, and drying at 100 ℃ for 12 to 14h 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.
4. The preparation method of the laminated glass heat-conducting heat-resisting EVA film according to claim 1, wherein the mass ratio of the composite heat-conducting heat-resisting powder, the tackifier and the EVA premix in the first step is 24-27: 7-9: 88.
5. The preparation method of the heat-conducting and heat-resisting EVA film for the laminated glass according to claim 1, wherein the EVA premix of the second step is prepared by uniformly stirring 68 to 75 parts by weight of an ethylene-vinyl acetate copolymer, 15 to 20 parts by weight of chlorosulfonated grafted EVA and 0.4 to 0.7 part by weight of dicumyl peroxide.
6. The method for preparing the heat-conducting and heat-resisting EVA film of the laminated glass according to claim 1, wherein the chlorosulfonated grafted EVA is prepared by the following steps: (1) Taking powdery EVA, putting the powdery EVA into a chlorination reaction kettle added with a mixed solvent of trichloromethane 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 to 9; the mixed solvent contains 0.04 to 0.1 percent of talcum powder dispersant, 0.003 to 0.005 percent of AIBN initiator and 0.05 to 0.1 percent of grafting monomer by weight of the mixed solvent, wherein the grafting monomer is maleic anhydride or methyl methacrylate; (2) graft chlorination: heating the reaction kettle to 70 ℃, introducing chlorine gas while stirring, wherein the temperature is 90-130 ℃, stirring for 1-3 hours, and controlling the pressure of the reaction kettle to be 0.4-0.6 MPa and the chlorination degree to be 5-7%; (3) And continuously preheating the mixed gas to 25 to 70 ℃, introducing the mixed gas into the reaction kettle, wherein the reaction pressure is 0.1 to 0.2MPa, the reaction temperature is 70 to 80 ℃, and the reaction temperature is 40 to 50min, and when the chlorine content is 17 to 18 percent, the sulfur content is as follows: and (3) discharging the material when the concentration is 0.5 to 1%, and performing solid-liquid separation, washing and drying to obtain the chlorosulfonated grafted EVA, wherein the mixed gas consists of chlorine and sulfur dioxide, the volume ratio of the chlorine to the sulfur dioxide is 1.2 to 0.3, and the adding speed of the mixed gas is 5 to 8% of the total adding amount per 10min.
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