CN116426109B - PC film, flame-retardant transparent fiber composite material and preparation method - Google Patents

PC film, flame-retardant transparent fiber composite material and preparation method Download PDF

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CN116426109B
CN116426109B CN202310516024.1A CN202310516024A CN116426109B CN 116426109 B CN116426109 B CN 116426109B CN 202310516024 A CN202310516024 A CN 202310516024A CN 116426109 B CN116426109 B CN 116426109B
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film
flame
fiber composite
flame retardant
transparent fiber
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CN116426109A (en
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马海丰
华国飞
陈增军
阳赛林
赵春生
夏云兰
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Shanghai Pincheng Holding Group Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/549—Silicon-containing compounds containing silicon in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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Abstract

The invention discloses a PC film, a flame-retardant transparent fiber composite material and a preparation method thereof, wherein the PC film comprises the following components: PC resin, nano catalyst, interface modifier, organic silicon flame retardant, poly (block-phosphonyloxy-carbonate) and antioxidant. The flame-retardant transparent composite fiber material consists of glass fibers and the PC film. The flame-retardant transparent fiber composite material prepared by the invention has higher flame retardance, heat resistance, light transmittance and tensile strength.

Description

PC film, flame-retardant transparent fiber composite material and preparation method
Technical Field
The invention relates to the field of PC materials, in particular to a PC film, a flame-retardant transparent fiber composite material and a preparation method thereof.
Background
The high-strength transparent glass is widely applied to aviation, military and medical high-energy ray protection devices, and at present, single glass components or double glass components are mostly used in photovoltaic components. Because of the large specific gravity of glass, more mounting structures need to be designed during mounting, so that the glass photovoltaic product cannot be used in a large area in a region with requirements on bearing, and the glass photovoltaic product is fragile under high stress, limited in design shape and size and difficult to replace and maintain after being damaged.
The light photovoltaic module has small overall thickness and easy installation, and is widely applied to buildings with load-bearing limitation requirements, but the battery piece is easy to crack and needs to be supported by using a composite material panel or a back panel. The surface and the back of most light photovoltaic modules are provided with continuous glass fiber reinforced structures, but because of the limitation of high light transmission, the composite material on the upper surface of the module is generally less than 0.2mm in thickness, so that the deformation of the module is still large in impact resistance, and the module is difficult to pass hail test. And because glass fiber belongs to a continuous phase in resin, the filled glass fiber cannot be used as a carbon forming center in combustion, and excessive flame retardant can cause further reduction of light transmittance of the product, so that the surface composite material of the target photovoltaic product cannot reach the flame retardant grade of GB8624B1 of the building. This greatly limits its application in the building field.
The polycarbonate honeycomb structure is used by CN 114864727A Gude Wei power supply technology (Guangde) limited company to realize ventilation and heat dissipation, namely, the structural strength is enhanced, the heat dissipation is improved, and the heat-resistant trouble is avoided, but the product can only be used as a backboard, the thickness of the product is large, and the light blocking rate of a single interface is more than 4%, so that the back can not realize light transmission.
The new energy science and technology company on WO2019006765A1 prepares transparent composite materials by taking synthetic acrylic resin as a resin base material and then presoaking powder on glass fibers, but the transparent composite materials have high light transmittance and excellent weather resistance, but the process of the transparent composite materials cannot be continuous due to the fact that the thermosetting resin synthesis is involved, the powder presoaking production process is complex, the natural carbon content of acrylic ester is low, the GB8624B1 flame retardance cannot be achieved, and the application of the transparent composite materials to buildings is greatly limited.
Disclosure of Invention
The technical problem to be solved by the invention is that the surface composite material of the existing photovoltaic product cannot reach the flame retardant grade of GB8624B1 of the building, and the application of the surface composite material of the existing photovoltaic product in the field of the building is greatly limited.
In order to solve the problem, in one aspect, the invention provides a PC film, which is composed of the following raw materials in parts by weight: 93.3 to 96.3 parts of PC resin, 0.3 to 0.5 part of nano catalyst, 1.1 to 2 parts of interface modifier, 0.1 to 1 part of organic silicon flame retardant, 2 to 3 parts of poly (block-phosphonyloxy-carbonate) and 0.1 to 1 part of antioxidant; wherein the nano catalyst is methyl methacrylate coated-silane coupled nano titanium dioxide.
Further, the weight average molecular weight of the PC resin is 22000-25000, and the molecular weight distribution is 1.25-1.7.
Further, the acrylic acid grafting rate in the methyl methacrylate coated-silane coupled nano titanium dioxide is 3% -5%, and the higher grafting rate can cause too thick interface layer and increase haze. And extracting by using a Soxhlet extractor and tetrahydrofuran as a solvent, and calculating the grafting rate according to the peak area of acrylic acid after extraction, drying and pressing. The acrylic ester and the nano titanium dioxide are mixed according to a certain proportion, the transmission IR peak area is tested from 1% wt. fraction to 10 wt. to obtain a standard curve, and then linear fitting is carried out on the standard curve.
Further, the preparation method of the methyl methacrylate coated-silane coupled nano titanium dioxide comprises the following steps:
stirring nano titanium dioxide in an absolute ethanol solution in a nitrogen atmosphere, and performing ultrasonic dispersion for a preset time after stirring to obtain an ultrasonic-dispersed nano titanium dioxide dispersion;
sequentially adding methyl methacrylate, a silane coupling agent, an initiator and an anti-agglomerating agent into the nano titanium dioxide dispersion liquid after ultrasonic dispersion, and stirring at a preset temperature for reaction for a preset time;
and (3) evaporating the solvent, distilling under reduced pressure and drying the stirred substance to obtain the methyl methacrylate coated-silane coupled nano titanium dioxide.
The concentration of the nano titanium dioxide dispersion liquid is 50-60g/L.
The ultrasonic dispersion time is 1-3h.
The dosage ratio of the nano titanium dioxide to the methyl methacrylate to the silane coupling agent to the initiator to the anti-caking agent is 500-600g:500-600mL:100-200mL:0.5-1g:2-5g.
The silane coupling agent is preferably methacryloxypropyl trimethoxysilane.
The initiator is preferably benzoyl peroxide.
The anticoagulant is preferably calcium phosphate.
The stirring reaction temperature is 80-90 ℃, and the stirring reaction time is 1-3h.
The methyl methacrylate coating-silane coupled nano titanium dioxide is ground by a pulverizer before being used.
Further, the interface modifier comprises 1 to 1.5 parts of small molecular interface modifier and 0.1 to 0.5 part of macromolecular interface modifier.
The small molecular interface modifier is at least one of hexaphenoxy cyclotriphosphazene and bisphenol A cyclophosphazene; the macromolecular interface modifier is at least one of polycaprolactone, alpha-methyl polycaprolactone and alpha-ethyl polycaprolactone.
Further, the mole fraction of diaryl phosphate in the poly (block-phosphonyloxy-carbonate) is between 10% and 20%, the mole fraction of phosphonyloxy is between 10% and 40%, and the mole fraction of polycarbonate units is between 40% and 80%.
Further, the organic silicon flame retardant is at least one of octaphenyl cyclotetrasiloxane, polysilaborane and derivatives thereof, crosslinked polydimethylsiloxane and derivatives thereof, methylphenyl siloxane and derivatives thereof, polyorganosiloxane silsesquioxane and cage silsesquioxane and derivatives thereof.
Further, the antioxidant comprises at least one of hindered phenol antioxidants and phosphite antioxidants.
On the other hand, the invention provides a flame-retardant transparent fiber composite material, which consists of glass fibers and the PC film.
In another aspect, the present invention provides a method of preparing a flame retardant transparent fiber composite, the method comprising:
blending and extruding the components according to the proportion to obtain PC particles, and then extruding the film;
and (3) carrying out hot pressing presoaking on the PC film and the glass fiber by using a continuous hot pressing method to obtain the flame-retardant transparent fiber composite material.
In another aspect, the invention provides an application of the flame-retardant transparent fiber composite material in photovoltaic module encapsulation or in the field of construction.
The invention has the following beneficial effects:
1. the flame-retardant transparent fiber composite material prepared by the invention has higher heat resistance and building flame retardance: the composite material achieves GB/8624B1 flame retardance and ensures high heat resistance, the relative temperature index RTI is above 110 ℃, the material requirement of IEC62788 on heat resistance and long service life of the packaging material is met, the glass fiber wick effect of the composite material is overcome, the carbon layer plays a role in isolating flame, and the carbon layer passes through GB8624B1 flame retardance grade and is used in building photovoltaic integrated components, such as the field of sound barriers.
2. The flame-retardant transparent fiber composite material prepared by the invention has high light transmittance, and the light transmittance of 2 layers of flame-retardant transparent fiber composite materials is more than 87.5% when being overlapped; and compared with the thermosetting epoxy composite material, the thermoplastic film prepreg method can be used for continuous production, and the preparation time cost and the energy consumption cost are both low.
3. The glass fiber uses continuous film presoaking, the yarn number and texture linear density of the fabric are easy to control under stretching, and high light transmittance stability can be maintained. The high-temperature surface can separate PC from semi-crystalline PCL and low-molecular hexaphenoxy cyclotriphosphazene in hot pressing, so that the surface tension (before corona) of the composite material is more than 40mN/m, and the subsequent use of POE or EVA adhesive films for packaging the composite material with fluorine films or PET with fluorine films is facilitated.
4. The PC film provided by the invention can not damage glass fibers in the presoaking process, and has less fiber scattering and fiber breaking conditions, so that the prepared flame-retardant transparent fiber composite material has high strength, the tensile strength can reach 300MPa, and the tensile modulus can reach 11GPa. Meanwhile, the addition of the interfacial agent can increase the infiltration of PC and glass fiber. During presoaking, the semi-crystalline PCL and the phenoxy cyclophosphazene are plasticized at the interface of the resin and the fiber, so that the composite material keeps better interfacial tension at high and low temperature impact (-40-85 ℃), and the light transmittance of the PC composite material is reduced because holes or silver lines are not generated due to large stress.
5. The flame-retardant transparent fiber composite material prepared by the invention has higher heat resistance: according to the invention, the flame retardant which does not reduce the heat resistance of the material and the prepared nano catalyst play a role of Lewis acid at high temperature, and the heat resistance can be greatly increased under the reinforcement of glass fibers, and the packaging assembly can pass a hot spot test at 165 ℃ for 4 hours.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully, and it is apparent that the embodiments described are only some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The embodiment of the invention provides a PC film, which consists of the following raw materials in parts by weight: 92.3 to 96.3 parts of PC resin, 0.3 to 0.5 part of nano catalyst, 1.1 to 2 parts of interface modifier, 0.1 to 1 part of organic silicon flame retardant, 2 to 3 parts of poly (block-phosphonyloxy-carbonate) and 0.1 to 1 part of antioxidant.
Optionally, the interface modifier comprises 1-1.5 parts of a small molecular interface modifier and 0.1-0.5 part of a high molecular interface modifier, wherein the small molecular interface modifier is hexaphenoxy cyclotriphosphazene (HPCTP), and the high molecular interface modifier is Polycaprolactone (PCL). Accordingly, the raw materials of the PC film can be as shown in table 1.
TABLE 1 raw materials for PC films
Material type Parts by weight
PC resin 93.3～96.3
Nanometer catalyst 0.3～0.5
Small molecule interface modifier 1～1.5
Polymer interface modifier 0.1～0.5
Organosilicon flame retardant 0.1～1
Poly (block-phosphonyloxy-carbonate) 2～3
Antioxidant 0.1～1
In the embodiment, PCL and phenoxy cyclotriphosphazene are used as interface modifiers, so that the infiltration of materials and glass fibers can be improved, holes for scattering light at the interface of resin and glass fibers can be reduced, and the light transmittance is improved by 1% -2%.
Alternatively, the weight average molecular weight of the PC (polycarbonate) resin is between 22000 and 25000, and the molecular weight distribution is between 1.25 and 1.7. Illustratively, the PC resin is synthesized by the phosgene method, having an end-capping rate above 97% wt, and a melt flow rate of 300 ℃/1.2kg mi=20 g/10min, i.e. 20g of melt per 10 minutes flowing through a standard die at 300 ℃ and a pressure of 1.2 kg.
Optionally, the nano catalyst is methyl methacrylate packageThe coated-silane coupled nano titanium dioxide, noted as: tiO (titanium dioxide) 2 -MA. The preparation method of the methyl methacrylate coated-silane coupled nano titanium dioxide comprises the following steps:
stirring nano titanium dioxide in an absolute ethanol solution in a nitrogen atmosphere, and performing ultrasonic dispersion for a preset time after stirring to obtain an ultrasonic-dispersed nano titanium dioxide dispersion; sequentially adding methyl methacrylate, a silane coupling agent, an initiator and an anti-agglomerating agent into the nano titanium dioxide dispersion liquid after ultrasonic dispersion, and stirring at a preset temperature for reaction for a preset time; and (3) evaporating the solvent, distilling under reduced pressure and drying the stirred substance to obtain the methyl methacrylate coated-silane coupled nano titanium dioxide.
Because the continuous fiber composite material has high flame retardance difficulty, the continuous fiber is self-formed into a phase, the resin has no dilution and isolation effect during combustion, and the resin cannot form a continuous carbon layer to further isolate flame, so that the heat release of the resin is high during testing GB8624, and the methyl methacrylate coated-silane coupled nano titanium dioxide is added into a resin formula to generate good barrier effect during combustion, wherein the FIGRA (0.2 MJ) is less than or equal to 120W/s, and the heat release is low THR (600) is less than or equal to 7.5MJ.
Illustratively, 500g of nano titanium dioxide (e.g., JWN-OR15, very micro-nano new material) may be stirred in 10L of absolute ethanol solution, after which it is dispersed ultrasonically for 1h; controlling the whole reaction to be carried out in nitrogen; ultrasonically dispersed TiO 2 The dispersion was added to a 15L reactor, followed by the sequential addition of 500ml of methyl methacrylate (e.g., 99.5% GC), 100ml of methacryloxypropyl trimethoxysilane (KH-570), 0.5g of benzoyl peroxide as an initiator, 3g of calcium phosphate as an anti-coagulant, and the reaction was stirred at 85℃for 2 hours. Recovering solvent by rotary evaporation after reaction, increasing concentration, and then performing reduced pressure distillation, drying at 100 ℃ for more than 1h after distillation to obtain methyl methacrylate coated-silane coupled nano titanium dioxide, which is recorded as TiO 2 MA-1 (grafting 3% peak area ratio), tiO2-MA-2 (grafting 5% peak area ratio). When in use, the powder is ground by a powder grinder, and the sieving residue rate of 50 μm is below 15%.
In this example, in order to increase the dispersion of nano titanium dioxide, a chemical suspension polymerization method is used, the nano titanium dioxide is coated with methyl methacrylate and a silane coupling agent, and the solvent used for suspension grafting is absolute ethanol, which can absorb the coupling agent for dehydration reaction. The grafting rate is reduced by controlling the concentration of the grafting monomer, and the size of the nano-dioxide of the methyl methacrylate coating-silane coupling is controlled below 50 mu m, so that the influence of the titanium dioxide on the light transmittance is reduced to the minimum.
Optionally, the mole fraction of diaryl phosphate in the poly (block-phosphonyloxy-carbonate) is between 10% and 20%, the mole fraction of phosphonyloxy is between 10% and 40%, and the mole fraction of polycarbonate units is between 40% and 80%. Optionally, the organic silicon flame retardant is at least one of octaphenyl cyclotetrasiloxane, polysilaborane and derivatives thereof, crosslinked polydimethylsiloxane and derivatives thereof, methyl phenyl siloxane and derivatives thereof, polyorganosiloxane silsesquioxane and cage silsesquioxane and derivatives thereof.
The haze is increased due to the defects of the resin matrix and the glass fiber, and the transparency of the finally obtained flame-retardant transparent fiber composite material can be ensured by using the transparent flame retardant copolyphosphate (namely poly (block-phosphonyloxy-carbonate)) and octaphenyl cyclotetrasiloxane as flame retardant systems. Since GB8624B1 is mainly tested for heat release, in PC substrates, the addition of other additive flame retardants in addition to halogen and filler flame retardants increases the heat release of the material and reduces the heat distortion temperature under load of the material. The flame retardant of the embodiment is mainly prepared from high molecular weight copolymerized phosphorus and octaphenyl cyclotetrasiloxane with lower reactivity, and the octaphenyl cyclotetrasiloxane diffuses to the surface of a material when heated to form a silicon-carbon layer, so that degradation is slowed down, and heat release during carbon formation is reduced. And simultaneously, nano titanium dioxide is matched and used as Lewis acid at high temperature to catalyze into carbon. The addition of nano titanium dioxide can reduce the addition amount of the copolymerization flame retardant by about 3 percent. The material can achieve the effect of low heat release under the condition of the least flame retardant addition, and the heat resistance of the material is improved.
Optionally, the antioxidant comprises at least one of a hindered phenolic antioxidant and a phosphite antioxidant. Illustratively, the weight ratio of hindered phenolic antioxidant to phosphite antioxidant is 3:2. Illustratively, the hindered phenolic antioxidant and the phosphite antioxidant may be antioxidants 1076/168.
The embodiment also provides a flame-retardant transparent fiber composite material, which consists of glass fibers and a PC film.
As an example, the preparation method of the PC film is as follows:
the PC film is obtained by blending and extruding the components according to the proportion by using a double-screw extruder at 260-280 ℃ to obtain PC particles and extruding the PC particles by using a single-screw extruder.
Illustratively, the PC film has a thickness of 0.1.+ -. 0.02mm.
The embodiment also provides a preparation method of the flame-retardant transparent fiber composite material, which comprises the following steps:
and (3) carrying out hot-pressing, presoaking and hot-pressing presoaking on the PC film and the glass fiber by using a continuous hot-pressing method, wherein the linear speed of 2m/min is adopted, and the pressure of a preheating section is 0.2 MPa: and (5) exhausting at 200 ℃ for 2 min. Then the mixture is introduced into a press, the temperature of the pressure is 1.2MPa and the temperature is 260 ℃ for 2min, and the linear velocity is 2m/min. The hot-pressing structure is a PC film, a fiber cloth and a PC film, the hot pressing adopts a polytetrafluoroethylene press, and the pressure between tetrafluoroethylene belts is controlled to be 1.2MPa by controlling the pressure, so that the single-layer flame-retardant transparent fiber composite material with the thickness of 0.2mm is obtained.
Illustratively, the glass fibers may be GF woven cloth, the specifications of which include, but are not limited to: ESC-307-HR, ESC307-K/HR, ESC-307-M4, and the like.
The refractive index matching property between the fibers and the resin, the refractive index difference of material shrinkage can cause refractive index change at different temperatures, especially when the fiber content is more than 40%, delta RI is less than 0.01, glass fibers with the refractive index similar to that of polycarbonate are selected, the refractive index difference between the resin and the glass fibers is ensured to be less than 0.01, the fiber cloth is presoaked by using a continuous film, the number of threads and the texture linear density of the fabric are easy to control under stretching, and higher light transmittance stability can be maintained.
The flame-retardant transparent fiber composite material prepared by different raw material proportions and the performance thereof are described below. Tables 2 and 3 are comparative tables of the ratios of raw materials in different examples and comparative examples, and tables 4 and 5 are comparative tables of the properties of the flame retardant transparent fiber composite materials prepared in different examples and comparative examples.
Table 2 comparison of raw material ratios in different examples and comparative examples
Table 3 shows the proportions of the raw materials in the different examples and comparative examples
TABLE 4 comparison of effects of flame retardant transparent fiber composites with different raw material ratios
Table 5 shows the comparison of the effects of the flame-retardant transparent fiber composite materials with different raw material ratios
Referring to tables 2 and 4, the flame retardant transparent fiber composite (e.g., example 1) to which the nanocatalyst and the polymeric interface modifier were added has a lower flame growth rate index FIGRA (0.2 MJ), a lower 600s total heat release amount THR (600 s), a lower 600s total smoke generation amount TSP (600 s), a higher tensile strength, and a better transmittance than the flame retardant transparent fiber composite (e.g., comparative example 0, comparative example 1, comparative example 2) to which the nanocatalyst and the polymeric interface modifier were not added. The reason for having the above excellent properties is that: in the embodiment of the invention, the methyl methacrylate coated-silane coupled nano titanium dioxide is used, a chemical suspension polymerization method is used for increasing the dispersion of the nano titanium dioxide, the nano titanium dioxide is coated by acrylic ester and a coupling agent, and the solvent used for suspension grafting is absolute ethyl alcohol and can absorb the coupling agent dehydrated by reaction. The grafting rate is reduced by controlling the concentration of the grafting monomer, and the size of the coated nano titanium dioxide is controlled below 50 mu m, so that the influence of the titanium dioxide on the light transmittance is reduced to the minimum. And PCL interface agent is used for improving the infiltration of the material and the glass fiber, reducing holes for scattering light at the interface of the resin and the glass fiber and improving the light transmittance by 1% -2%. In addition, the addition of the coated nanomaterial to the resin formulation produces a good barrier upon combustion with a FIGRA (0.2 MJ) of 120W/s or less and a low heat release THR (600) of 7.5MJ or less.
With continued reference to tables 2 and 4, the flame retardant transparent fiber composite (e.g., example 2) with the addition of poly (block-phosphonyloxy-carbonate) had a lower flame growth rate index FIGRA (0.2 MJ), and a lower 600s total heat release THR (600 s), a lower 600s total smoke generation TSP (600 s), a higher tensile strength, and a better transparency than the flame retardant transparent fiber composite (e.g., comparative example 3) without the addition of poly (block-phosphonyloxy-carbonate). The reason for having the above excellent properties is that: the defects of the resin matrix and the glass fiber can cause the increase of haze, and the transparent flame retardant copolyphosphate (namely poly (block-phosphonyloxy-carbonate)) and octaphenyl cyclotetrasiloxane are used as flame retardant systems to ensure transparency. In addition, since GB8624B1 is mainly tested for heat release, the addition of other additive flame retardants in addition to halogen and filler flame retardants in PC substrates increases the heat release of the material and reduces the heat distortion temperature under load of the material. The flame retardant disclosed by the embodiment of the invention is mainly prepared from high-molecular-weight copolymerized phosphorus (namely poly (block-phosphonyl oxygen-carbonate)) and octaphenyl cyclotetrasiloxane with lower reactivity, and the copolymerized phosphorus is diffused to the surface of a material when heated to form a silicon-carbon layer, so that degradation is slowed down, and heat release during carbon formation is reduced. And simultaneously, nano titanium dioxide is matched and used as Lewis acid at high temperature to catalyze into carbon. The addition of nano titanium dioxide can reduce the addition amount of the copolymerization flame retardant by about 3 percent. The material can achieve the effect of low heat release under the condition of the least flame retardant addition, and the heat resistance of the material is improved.
Referring to tables 3 and 5, the flame retardant transparent fiber composite (e.g., example 3) to which the silicone flame retardant was added and the flame retardant transparent fiber composite (e.g., comparative example 4) to which the silicone flame retardant was not added were lower in the flame growth rate index FIGRA (0.2 MJ), and lower in the total heat release amount THR (600 s) of 600s, lower in the total smoke generation amount TSP (600 s), higher in tensile strength, and better in transmittance. The reason for having the above excellent properties is that: the flame retardant disclosed by the embodiment of the invention is mainly prepared from high-molecular-weight copolymerized phosphorus (namely poly (block-phosphonyl oxygen-carbonate)) and octaphenyl cyclotetrasiloxane with lower reactivity, and the copolymerized phosphorus is diffused to the surface of a material when heated to form a silicon-carbon layer, so that degradation is slowed down, and heat release during carbon formation is reduced. And simultaneously, nano titanium dioxide is matched and used as Lewis acid at high temperature to catalyze into carbon. The addition of nano titanium dioxide can reduce the addition amount of the copolymerization flame retardant by about 3 percent. The material can achieve the effect of low heat release under the condition of the least flame retardant addition, and the heat resistance of the material is improved.
Referring to tables 3 and 5, the flame retardant transparent fiber composite (e.g., example 4) to which the small molecular interface modifier and the high molecular interface modifier were added has a low flame growth rate index FIGRA (0.2 MJ), a low total heat release amount THR (600 s) of 600s, a low total smoke generation amount TSP (600 s) of 600s, a high tensile strength and a high tensile modulus, and a good transmittance. The reason for having the above excellent properties is that: PCL and phenoxy cyclotriphosphazene are used as interface modifiers, so that the infiltration of materials and glass fibers is improved, holes for scattering light at the interface of resin and glass fibers are reduced, and the light transmittance is improved by 1% -2%.
In summary, the embodiment of the invention is based on the demand of the photovoltaic product on the transparent composite material, and is used for manufacturing the fireproof flame-retardant PC-based transparent composite material for packaging the photovoltaic panel and the backboard, wherein the strength of the composite material can reach 300MPa, the tensile modulus can reach 11GPa, the flame retardance is good, the flame retardance demand of GB8624B1 can be met, the light transmittance of 0.25mm is 87.1%, the heat resistance is high, the softening point of 50N micro-card is 140 ℃, and the component can meet the IEC61730 and IEC61215 hail test and hot spot test.
The embodiment of the invention also provides application of the flame-retardant transparent fiber composite material in the photovoltaic module packaging or in the building field.
The foregoing disclosure is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.

Claims (8)

1. The PC film is characterized by comprising the following raw materials in parts by weight: 93.3 to 96.3 parts of PC resin, 0.3 to 0.5 part of nano catalyst, 1.1 to 2 parts of interface modifier, 0.1 to 1 part of organic silicon flame retardant, 2 to 3 parts of poly (block-phosphonyloxy-carbonate) and 0.1 to 1 part of antioxidant; wherein the nano catalyst is methyl methacrylate coated-silane coupled nano titanium dioxide; the organic silicon flame retardant is at least one of octaphenyl cyclotetrasiloxane, polysilaborane and derivatives thereof, crosslinked polydimethylsiloxane and derivatives thereof, methylphenyl siloxane and derivatives thereof, polysilsesquioxane and cage-type silsesquioxane and derivatives thereof; the interface modifier comprises 1 to 1.5 parts of small molecular interface modifier and 0.1 to 0.5 part of macromolecular interface modifier; the small molecular interface modifier is at least one of hexaphenoxy cyclotriphosphazene and bisphenol A cyclophosphazene; the macromolecular interface modifier is at least one of polycaprolactone, alpha-methyl polycaprolactone and alpha-ethyl polycaprolactone.
2. The PC film according to claim 1, wherein the PC resin has a weight average molecular weight of 22000 to 25000 and a molecular weight distribution of 1.25 to 1.7.
3. The PC film according to claim 1, wherein the acrylic grafting ratio in the methyl methacrylate coated-silane coupled nano titanium dioxide is 3% to 5%.
4. The PC film of claim 1 wherein the mole fraction of diaryl phosphate in the poly (block-phosphonooxy-carbonate) is between 10% and 20%, the mole fraction of phosphonooxy is between 10% and 40%, and the mole fraction of polycarbonate units is between 40% and 80%.
5. The PC film of claim 1 wherein the antioxidant comprises at least one of a hindered phenolic antioxidant and a phosphite antioxidant.
6. A flame retardant transparent fiber composite, characterized in that the flame retardant transparent fiber composite consists of glass fibers and the PC film of any one of claims 1 to 5.
7. A method of preparing the flame retardant transparent fiber composite of claim 6, wherein the method comprises:
blending and extruding the components according to the proportion to obtain PC particles, and extruding the film; and (3) carrying out hot pressing presoaking on the PC film and the glass fiber by using a continuous hot pressing method to obtain the flame-retardant transparent fiber composite material.
8. Use of the flame retardant transparent fiber composite of claim 6 in photovoltaic module packaging or in the field of construction.
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