A hyperbranched flame-retardant compatibilizer, a preparation method, a flame-retardant high-modulus polycarbonate, a preparation method and an application

Abstract

The application discloses a hyperbranched flame-retardant compatilizer, a preparation method thereof, a flame-retardant high-modulus polycarbonate, a preparation method and application thereof. The structural formula of the hyperbranched flame-retardant compatilizer is: The flame-retardant high-modulus polycarbonate comprises the following components: polycarbonate 70-90 parts, antioxidant 0.1-0.5 parts, hyperbranched flame-retardant compatilizer 1-10 parts, lubricant 0.2-0.5 parts and glass fiber 5-40 parts. The hyperbranched flame-retardant compatilizer can improve the interfacial bonding force and two-phase compatibility between the polycarbonate resin and the glass fiber; meanwhile, the modified glass fiber reinforced polycarbonate material has the advantages of excellent flame-retardant performance, good processing performance and low cost, and can be widely applied to the rail transit field with high requirements on mechanics and flame retardation.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a hyperbranched flame retardant compatibilizer and its preparation method, a flame retardant high modulus polycarbonate and its preparation method and application. Background Technology

[0002] Polycarbonate (PC) is widely used due to its excellent physical properties, high impact strength, and good dimensional stability. However, in some cases, the material's rigidity and dimensional stability are slightly insufficient. To address this issue, glass fiber reinforcement modification is commonly employed. Modified PC resin exhibits excellent flexural modulus and heat resistance, making it suitable for components subjected to continuous loads or heat resistance. Flame retardant modification can effectively increase the added value of such composite materials and broaden their application areas, showing great market potential. However, due to certain compatibility issues between the fiber and the matrix, the "wick effect" is particularly pronounced when the composite material burns. The matrix resin melts, softens, and decomposes, wetting and rapidly flowing directionally along the glass fiber surface into the flame zone. Therefore, blocking the fuel transport channel at the glass fiber / matrix interface can effectively solve the problem of the difficulty in flame retardancy of glass fiber reinforced thermoplastic composites.

[0003] Currently, only by simultaneously introducing additives with both flame-retardant and compatibilizing effects can the mechanical and flame-retardant properties of composite materials be improved at the same time. However, the development of such interfacial compatibilizing flame-retardant additives still faces a series of problems, including complex synthesis steps, low yield, and difficulties in fiber surface treatment. Summary of the Invention

[0004] To address the problems existing in the prior art, the present invention provides a hyperbranched flame retardant compatibilizer and its preparation method, which achieves enhanced performance and excellent flowability and flame retardant modification effects without significantly altering the other properties of polycarbonate.

[0005] Another object of the present invention is to provide flame-retardant high-modulus polycarbonate containing such hyperbranched flame-retardant compatibilizer, as well as its preparation method and application.

[0006] To achieve the above-mentioned objectives, the technical solution adopted by the present invention is as follows:

[0007] A hyperbranched flame retardant compatibilizer having the structure of formula (I):

[0008]

[0009] On the other hand, a method for preparing the aforementioned hyperbranched flame retardant compatibilizer includes the following steps:

[0010] (1) Dissolve 8-12 parts by weight of styrene, 1-5 parts by weight of azobisisobutyronitrile and 2-8 parts by weight of p-vinylbenzylthiol in 60-80 parts by weight of aromatic hydrocarbon to prepare a mixed solution of monomer and initiator.

[0011] (2) Add 3-6 parts by mass of maleic anhydride, 1-2 parts by mass of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 3-5 parts by mass of p-aminobenzenesulfonic acid and 50-70 parts by mass of aromatic hydrocarbon to a four-necked flask. After complete dissolution, slowly add the mixed solution from step (1) while stirring. Finally, the reaction yields a hyperbranched flame retardant compatibilizer.

[0012] In steps (1) and (2) of this invention, the aromatic hydrocarbon is selected from one or a combination of several of benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, and mixed aromatic hydrocarbons, preferably toluene;

[0013] In step (2) of the present invention, the reaction temperature is 70-140℃, for example 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, etc., and the reaction time is 8-10h, for example 8h, 9h, 10h, etc.;

[0014] In step (2) of this invention, the mass ratio of the sum of the masses of maleic anhydride, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, p-aminobenzenesulfonic acid, and aromatic hydrocarbons to the mass ratio of the mixed solution in step (1) is 3 to 7:1.

[0015] As a preferred embodiment, step (2) further includes a post-processing step, for example, the following steps: adding a certain amount of toluene solvent to dissolve, refluxing and filtering while hot, washing several times with toluene and tetrahydrofuran to obtain a solid, drying under vacuum to obtain the target compound. After the reaction is complete, the product is filtered and washed several times with hot toluene, then dissolved in acetone, and finally separated by precipitation with ethanol. This operation is repeated 3 times, and then dried in a vacuum drying oven at 30°C to finally obtain the hyperbranched flame retardant compatibilizer compound.

[0016] The reaction process of the hyperbranched flame retardant compatibilizer of the present invention is illustrated below:

[0017]

[0018] In another aspect of the present invention, a flame-retardant high-modulus polycarbonate is prepared from raw materials comprising the following components, in parts by weight:

[0019] 70-90 parts of polycarbonate, such as 70 parts, 72 parts, 75 parts, 78 parts, 80 parts, 83 parts, 85 parts, 87 parts, 89 parts, 90 parts, etc.;

[0020] Antioxidant 0.1-0.5 parts, such as 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, etc.;

[0021] Hyperbranched flame retardant compatibilizer 1-10 parts, such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.;

[0022] Lubricant 0.2-0.5 parts, for example 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, etc.;

[0023] Glass fiber 5-40 parts, such as 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, etc.;

[0024] The hyperbranched flame retardant compatibilizer is the aforementioned hyperbranched flame retardant compatibilizer or the hyperbranched flame retardant compatibilizer prepared by the aforementioned preparation method.

[0025] In this invention, the polycarbonate (PC) is selected from one or more of aromatic polycarbonate, aliphatic polycarbonate, and aromatic-aliphatic polycarbonate, preferably bisphenol A type polycarbonate; preferably, under test conditions of 300°C and a load of 1.2 kg, the melt flow index of the polycarbonate is 6 to 30 cm⁻¹. 3 Between 10 min and 6-20 cm, preferably between 10 min and 6-20 cm. 3 Between 10 min and 6-10 cm, more preferably between 6 and 10 min. 3 Between 10 minutes.

[0026] In this invention, the antioxidant is selected from one or a combination of two or more of hindered phenols, phosphites, thioesters, benzofurans, acryloyl-modified phenols, and hydroxylamines. More preferably, the antioxidant is a mixture of hindered phenolic antioxidants and phosphite antioxidants, with a weight ratio of hindered phenolic antioxidant to phosphite antioxidant of 1 / 5 to 1, such as 1:5, 1:4, 1:3, 1:2, 1:1, etc.

[0027] In this invention, the lubricant is one or a combination of pentaerythritol stearate, bis-stearamide lubricant, or PE wax, preferably pentaerythritol stearate (PETS).

[0028] In this invention, the glass fiber is a commercially available glass fiber with an average diameter of 6 to 20 μm, such as 6 μm, 7 μm, 8 μm, 10 μm, 13 μm, 15 μm, 18 μm, 20 μm, etc.; preferably 10 to 16 μm.

[0029] The polycarbonate composition of the present invention can selectively use the above-mentioned additives according to the product performance characteristics. For example, additive screening can be used to improve the processing and flame retardant properties of the glass fiber reinforced polycarbonate composition.

[0030] The polycarbonate of the present invention can also be processed with other processing aids, such as antibacterial agents and leveling agents, depending on the processing requirements. These are conventional techniques for those skilled in the art and will not be elaborated here.

[0031] In another aspect of the present invention, a method for preparing the above-mentioned polycarbonate includes the following steps:

[0032] (1) A master powder was obtained by mixing hyperbranched flame retardant compatibilizer with a portion of polycarbonate;

[0033] (2) Mix the masterbatch from step (1) with the remaining polycarbonate, antioxidant and lubricant to obtain a premix;

[0034] (3) Add the premix and glass fiber from step (2) to an extruder for extrusion granulation to obtain flame-retardant high-modulus polycarbonate blend granules;

[0035] The polycarbonate raw material is added in two steps, and the mass ratio of the addition in step (1) to step (2) is 1:1 to 30, for example, 1:1, 1:5:1:10, 1:15, 1:20, 1:25, 1:30, etc., preferably 1:5 to 20.

[0036] In step (2), the mixing process is carried out at room temperature, and the stirring temperature is controlled below 40°C, for example, 25°C. The mixture is added to a mixing machine (e.g., a high-speed mixer) for stirring to obtain a premix. The mixing speed is 20-100 r / min, for example, 20 r / min, 30 r / min, 40 r / min, 50 r / min, 60 r / min, 70 r / min, 80 r / min, 90 r / min, 100 r / min, etc., preferably 40-80 r / min. The mixing time is 15-60 min, for example, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, etc., preferably 20-40 min.

[0037] In step (3), the extrusion is preferably performed using a twin-screw extruder. The temperature of the extruder's conveying section is 230-280°C, for example, 250°C or 270°C; the temperature of the plasticizing section is 250-290°C, for example, 260°C or 285°C; the temperature of the metering section is 260-300°C, for example, 265°C or 295°C; the screw speed is controlled at 200-600 rpm, for example, 250 rpm or 400 rpm, preferably 250 rpm to 450 rpm; and the vacuum device of the twin-screw metering section is controlled at -0.9 to -0.5 bar.

[0038] In another aspect, the present invention provides the use of the above-described polycarbonate composition or the polycarbonate composition obtained by the above preparation method in flame-retardant high-modulus materials, which can be widely used in the rail transit field where mechanical and flame-retardant requirements are high.

[0039] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0040] The novel hyperbranched flame retardant compatibilizer of the present invention can further improve the mechanical properties of glass fiber reinforced PC while also having good flame retardancy.

[0041] The preparation method of the polycarbonate composition of the present invention achieves good dispersion of glass fiber in polycarbonate resin by adding hyperbranched flame retardant compatibilizer, thus ensuring the stability of product quality. Detailed Implementation

[0042] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0043] The raw materials used in the following embodiments and comparative examples are as follows:

[0044] Polycarbonate (PC): Clarnate 2100 (MFI=10), purchased from Wanhua Chemical Group Co., Ltd.;

[0045] Glass fiber-1: ECS13-4.5-510H (average diameter 13μm), purchased from China Jushi Co., Ltd.;

[0046] Glass fiber-2: ECS13-4.5-510 (average diameter 13μm), purchased from China Jushi Co., Ltd.;

[0047] Glass fiber-3: ECS13-3.0-T442 (average diameter 13μm), purchased from Taishan Fiberglass Co., Ltd.;

[0048] Conventional compatibilizer: styrene-maleic anhydride copolymer, maleic anhydride content 25%, purchased from Polyscope;

[0049] Hindered phenolic antioxidants: purchased from BASF Chemicals Ltd.;

[0050] Phosphite antioxidants: purchased from BASF Chemicals Ltd.;

[0051] Pentaerythritol stearate (PETS): Purchased from BASF Chemicals Ltd.;

[0052] p-Vinylbenzylthiol: purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0053] Styrene: Purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0054] Azobisisobutyronitrile (AIBN): Purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0055] Maleic anhydride: purchased from BASF Chemicals Ltd.;

[0056] Acetone: purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0057] Toluene: purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0058] Ethanol: Purchased from Aladdin Reagent Co., Ltd.;

[0059] 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide: purchased from Chengdu Aikeda Chemical Reagent Co., Ltd.;

[0060] p-Aminobenzenesulfonic acid: purchased from Aladdin Reagent Co., Ltd.

[0061] Preparation Example 1:

[0062] (1) Dissolve 10.2 parts by mass of styrene, 2.8 parts by mass of azobisisobutyronitrile and 5.4 parts by mass of p-vinylbenzylthiol in 80 parts by mass of toluene to prepare a monomer and initiator mixed solution.

[0063] (2) Accurately weigh 5.1 parts by mass of maleic anhydride and 70 parts by mass of toluene into a four-necked flask equipped with a condenser. Stir at 50°C until the maleic anhydride is completely dissolved, then raise the temperature to 70°C. Add the previously prepared mixture dropwise into the four-necked flask at a rate of 5 parts by mass / min and maintain the temperature for 6 hours. Under nitrogen protection, add 1.5 parts by mass of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 4 parts by mass of p-aminobenzenesulfonic acid into the four-necked flask. Raise the temperature to 135°C and react for 8–10 hours. Cool to 100°C, add a certain amount of toluene solvent, reflux for 1.5 hours, and filter while hot. Wash the filter cake with toluene several times to obtain a solid. Dry under vacuum to obtain the target compound. After the reaction was completed, the product was filtered and washed several times with hot toluene, then dissolved in acetone, and finally separated by precipitation with ethanol. This process was repeated 3 times. The product was then dried in a vacuum drying oven at 30°C to obtain hyperbranched flame retardant compatibilizer-1.

[0064] Preparation Example 2:

[0065] (1) Dissolve 8.1 parts by weight of styrene, 1.4 parts by weight of azobisisobutyronitrile and 2.8 parts by weight of p-vinylbenzylthiol in 80 parts by weight of toluene to prepare a monomer and initiator mixed solution.

[0066] (2) Accurately weigh 3.2 parts by mass of maleic anhydride and 70 parts by mass of toluene into a four-necked flask equipped with a condenser. Stir at 50°C until the maleic anhydride is completely dissolved, then raise the temperature to 70°C. Add the previously prepared mixture dropwise into the four-necked flask at a rate of 5 parts by mass / min and maintain the temperature for 6 hours. Under nitrogen protection, add 1 part by mass of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 3 parts by mass of p-aminobenzenesulfonic acid into the four-necked flask. Raise the temperature to 135°C and react for 8-10 hours. Cool down to 100°C, add a certain amount of toluene solvent, reflux for 1.5 hours, and filter while hot. Wash the filter cake with toluene several times to obtain a solid. Dry under vacuum to obtain the target compound. After the reaction was completed, the product was filtered and washed several times with hot toluene, then dissolved in acetone, and finally separated by precipitation with ethanol. This process was repeated 3 times. The product was then dried in a vacuum drying oven at 30°C to obtain hyperbranched flame retardant compatibilizer-2.

[0067] Preparation Example 3:

[0068] (1) Dissolve 11.7 parts by mass of styrene, 4.7 parts by mass of azobisisobutyronitrile and 7.8 parts by mass of p-vinylbenzylthiol in 80 parts by mass of toluene to prepare a monomer and initiator mixed solution.

[0069] (2) Accurately weigh 5.8 parts by mass of maleic anhydride and 70 parts by mass of toluene into a four-necked flask equipped with a condenser. Stir at 50°C until the maleic anhydride is completely dissolved, then raise the temperature to 70°C. Add the previously prepared mixture dropwise into the four-necked flask at a rate of 5 parts by mass / min and maintain the temperature for 6 hours. Under nitrogen protection, add 2 parts by mass of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 5 parts by mass of p-aminobenzenesulfonic acid into the four-necked flask. Raise the temperature to 135°C and react for 8-10 hours. Cool down to 100°C, add a certain amount of toluene solvent, reflux for 1.5 hours, and filter while hot. Wash the filter cake with toluene several times to obtain a solid. Dry under vacuum to obtain the target compound. After the reaction was completed, the product was filtered and washed several times with hot toluene, then dissolved in acetone, and finally separated by precipitation with ethanol. This process was repeated 3 times. The product was then dried in a vacuum drying oven at 30°C to obtain hyperbranched flame retardant compatibilizer-3.

[0070] Characterization of hyperbranched flame retardant compatibilizers:

[0071] FTIR: The synthesized copolymer hyperbranched flame retardant compatibilizer was analyzed at a wavenumber of 1775 cm⁻¹. -1 and 1852cm -1 Absorption peaks for the symmetric and antisymmetric stretching vibrations of the C=O bond in acid anhydrides appeared at 1775 cm⁻¹. -1 The low-frequency absorption peak ratio at 1852 cm⁻¹ -1 The high-frequency absorption peak intensity at 1450 cm⁻¹ indicates that the obtained compound contains a cyclic acid anhydride; -1 The absorption peak at 701 cm⁻¹ is the absorption peak of the in-plane stretching vibration of the C=C bond in the benzene ring; -1 and 1074cm -1 The absorption peaks at 3021 cm⁻¹ correspond to the out-of-plane and in-plane bending vibration absorption peaks of the CH bond on the benzene ring, respectively; -1 The absorption peak at 2918 cm⁻¹ corresponds to the stretching vibration of the CH bond on the benzene ring. -1 The absorption peak at 2562 cm⁻¹ corresponds to the stretching vibration of the -CH₂ bond on the benzene ring. The hyperbranched flame retardant compatibilizer exhibits this absorption at 2562 cm⁻¹. -1 No absorption peak for thiol groups was observed at 1221 cm⁻¹, while at 1221 cm⁻¹... -1 An absorption peak for the CS bond was observed. In conclusion, the obtained copolymer is determined to be a hyperbranched flame-retardant compatibilizer.

[0072] Intrinsic viscosity: To further characterize the structure of the hyperbranched flame retardant compatibilizer, its intrinsic viscosity was measured using an Ubbelohde viscometer, and the relative viscosity lnη was obtained. r / C, Specific viscosity η sp Relationship between / C and relative concentration C: lnη r / CC and η spThe / CC curves almost overlap and are parallel to the X-axis, from which the specific viscosity η can be derived. sp The relationship between concentration C and intrinsic viscosity [η] is: η sp / C = [η]. η sp =η r Substituting -1 into the above equation, we get η r The relationship between C and [η]: η r =1+[η]C, which obeys the Einstein viscosity equation. Therefore, the above characteristics indicate that the hyperbranched flame retardant compatibilizer of the present invention is a near-spherical macromolecular form, which further proves from the side that the synthesized compatibilizer has a hyperbranched structure.

[0073] Example 1

[0074] The method for preparing the polycarbonate composition includes the following steps:

[0075] (1) Put 1 kg of hyperbranched flame retardant compatibilizer-1 and 10 kg of polycarbonate 2100 into a high-speed mixer and mix them evenly at 30°C to obtain master powder.

[0076] (2) Add the master powder from step (1) to 78.4 kg of polycarbonate 2100, 0.4 kg of antioxidant and 0.2 kg of lubricant PETS in a high-speed mixer and mix for 30 min at 30°C and 80 r / min to obtain a premix.

[0077] (3) Add the premix to the twin-screw extruder, and at the same time add 10kg of glass fiber (ECS13-4.5-510H) to the extruder using a side feeder. Control the temperature of the conveying section of the twin-screw extruder to 260℃, the temperature of the plasticizing section to 280℃, and the temperature of the metering section to 290℃. Control the screw speed to 300rpm. Control the vacuum device of the metering section of the twin-screw extruder to -0.9bar to -0.5bar. After extrusion, drawing, water cooling, air drying, pelletizing, and drying, the blended granules of the flame-retardant high-modulus polycarbonate composition can be obtained.

[0078] Example 2

[0079] The method for preparing the polycarbonate composition includes the following steps:

[0080] (1) Put 10 kg of hyperbranched flame retardant compatibilizer-1 and 10 kg of polycarbonate 2100 into a high-speed mixer and mix them evenly at 30°C to obtain master powder.

[0081] (2) Add the master powder from step (1) to 69.1 kg of polycarbonate 2100, 0.4 kg of antioxidant and 0.2 kg of lubricant PETS in a high-speed mixer and mix for 30 min at 30°C and 80 r / min to obtain a premix.

[0082] (3) Add the premix to the twin-screw extruder, and at the same time add 10 kg of glass fiber (ECS13-4.5-510H) to the extruder using a side feeder. Control the temperature of the conveying section of the twin-screw extruder to 260°C, the temperature of the plasticizing section to 280°C, and the temperature of the metering section to 290°C. Control the screw speed to 300 rpm. Control the vacuum device of the metering section of the twin-screw extruder to -0.9 bar to -0.5 bar. After extrusion, drawing, water cooling, air drying, pelletizing, and drying, the blended granules of the flame-retardant high-modulus polycarbonate composition can be obtained.

[0083] Example 3

[0084] The method for preparing the polycarbonate composition includes the following steps:

[0085] (1) Put 6 kg of hyperbranched flame retardant compatibilizer-1 and 10 kg of polycarbonate 2100 into a high-speed mixer and mix them evenly at 30°C to obtain master powder.

[0086] (2) Add the master powder from step (1) to 73.4 kg of polycarbonate 2100, 0.4 kg of antioxidant and 0.2 kg of lubricant PETS in a high-speed mixer and mix for 30 min at 30°C and 80 r / min to obtain a premix.

[0087] (3) Add the premix to the twin-screw extruder, and at the same time add 10 kg of glass fiber (ECS13-4.5-510H) to the extruder using a side feeder. Control the temperature of the conveying section of the twin-screw extruder to 260°C, the temperature of the plasticizing section to 280°C, and the temperature of the metering section to 290°C. Control the screw speed to 300 rpm. Control the vacuum device of the metering section of the twin-screw extruder to -0.9 bar to -0.5 bar. After extrusion, drawing, water cooling, air drying, pelletizing, and drying, the blended granules of the flame-retardant high-modulus polycarbonate composition can be obtained.

[0088] Example 4

[0089] The method for preparing the polycarbonate composition includes the following steps:

[0090] (1) Put 6 kg of hyperbranched flame retardant compatibilizer-1 and 10 kg of polycarbonate 2100 into a high-speed mixer and mix them evenly at 30°C to obtain master powder.

[0091] (2) Add the master powder from step (1) to 68.4 kg of polycarbonate 2100, 0.4 kg of antioxidant and 0.2 kg of lubricant PETS in a high-speed mixer and mix for 30 min at 30°C and 80 r / min to obtain a premix.

[0092] (3) Add the premix to the twin-screw extruder, and at the same time add 15kg of glass fiber (ECS13-4.5-510H) to the extruder using a side feeder. Control the temperature of the conveying section of the twin-screw extruder to 260℃, the temperature of the plasticizing section to 280℃, and the temperature of the metering section to 290℃. Control the screw speed to 300rpm and control the vacuum device of the metering section of the twin-screw extruder to -0.9bar to -0.5bar. After extrusion, drawing, water cooling, air drying, pelletizing and drying, the blended granules of the flame-retardant high-modulus polycarbonate composition can be obtained.

[0093] Example 5

[0094] The method for preparing the polycarbonate composition includes the following steps:

[0095] (1) Put 6 kg of hyperbranched flame retardant compatibilizer-1 and 10 kg of polycarbonate 2100 into a high-speed mixer and mix them evenly at 30°C to obtain master powder.

[0096] (2) Add the master powder from step (1) to 63.4 kg of polycarbonate 2100, 0.4 kg of antioxidant and 0.2 kg of lubricant PETS in a high-speed mixer and mix for 30 min at 30°C and 80 r / min to obtain a premix.

[0097] (3) Add the premix to the twin-screw extruder, and at the same time add 20kg of glass fiber (ECS13-4.5-510H) to the extruder using a side feeder. Control the temperature of the conveying section of the twin-screw extruder to 260℃, the temperature of the plasticizing section to 280℃, and the temperature of the metering section to 290℃. Control the screw speed to 300rpm and control the vacuum device of the metering section of the twin-screw extruder to -0.9bar to -0.5bar. After extrusion, drawing, water cooling, air drying, pelletizing and drying, the blended granules of the flame-retardant high-modulus polycarbonate composition can be obtained.

[0098] Example 6

[0099] The method for preparing the polycarbonate composition includes the following steps:

[0100] (1) Put 6 kg of hyperbranched flame retardant compatibilizer-1 and 10 kg of polycarbonate 2100 into a high-speed mixer and mix them evenly at 30°C to obtain master powder.

[0101] (2) Add the master powder from step (1) to 73.4 kg of polycarbonate 2100, 0.4 kg of antioxidant and 0.2 kg of lubricant PETS in a high-speed mixer and mix for 30 min at 30°C and 80 r / min to obtain a premix.

[0102] (3) Add the premix to the twin-screw extruder, and at the same time add 10 kg of glass fiber (ECS13-4.5-510) to the extruder using a side feeder. Control the temperature of the conveying section of the twin-screw extruder to 260°C, the temperature of the plasticizing section to 280°C, and the temperature of the metering section to 290°C. Control the screw speed to 300 rpm. Control the vacuum device of the metering section of the twin-screw extruder to -0.9 bar to -0.5 bar. After extrusion, drawing, water cooling, air drying, pelletizing, and drying, the blended granules of the flame-retardant high-modulus polycarbonate composition can be obtained.

[0103] Example 7

[0104] The method for preparing the polycarbonate composition includes the following steps:

[0105] (1) Put 6 kg of hyperbranched flame retardant compatibilizer-1 and 10 kg of polycarbonate 2100 into a high-speed mixer and mix them evenly at 30°C to obtain master powder.

[0106] (2) Add the master powder from step (1) to 73.4 kg of polycarbonate 2100, 0.4 kg of antioxidant and 0.2 kg of lubricant PETS in a high-speed mixer and mix for 30 min at 30°C and 80 r / min to obtain a premix.

[0107] (3) Add the premix to the twin-screw extruder, and at the same time add 10 kg of glass fiber (ECS13-3.0-T442) to the extruder using a side feeder. Control the temperature of the conveying section of the twin-screw extruder to 260°C, the temperature of the plasticizing section to 280°C, and the temperature of the metering section to 290°C. Control the screw speed to 300 rpm and control the vacuum device of the metering section of the twin-screw extruder to -0.9 bar to -0.5 bar. After extrusion, drawing, water cooling, air drying, pelletizing, and drying, the blended granules of the flame-retardant high-modulus polycarbonate composition can be obtained.

[0108] Example 8

[0109] The method for preparing the polycarbonate composition includes the following steps:

[0110] (1) Put 6 kg of hyperbranched flame retardant compatibilizer-2 and 10 kg of polycarbonate 2100 into a high-speed mixer and mix them evenly at 30°C to obtain master powder.

[0111] (2) Add the master powder from step (1) to 73.4 kg of polycarbonate 2100, 0.4 kg of antioxidant and 0.2 kg of lubricant PETS in a high-speed mixer and mix for 30 min at 30°C and 80 r / min to obtain a premix.

[0112] (3) Add the premix to the twin-screw extruder, and at the same time add 10 kg of glass fiber (ECS13-4.5-510H) to the extruder using a side feeder. Control the temperature of the conveying section of the twin-screw extruder to 260°C, the temperature of the plasticizing section to 280°C, and the temperature of the metering section to 290°C. Control the screw speed to 300 rpm. Control the vacuum device of the metering section of the twin-screw extruder to -0.9 bar to -0.5 bar. After extrusion, drawing, water cooling, air drying, pelletizing, and drying, the blended granules of the flame-retardant high-modulus polycarbonate composition can be obtained.

[0113] Example 9

[0114] The method for preparing the polycarbonate composition includes the following steps:

[0115] (1) Put 6 kg of hyperbranched flame retardant compatibilizer-3 and 10 kg of polycarbonate 2100 into a high-speed mixer and mix them evenly at 30°C to obtain master powder.

[0116] (2) Add the master powder from step (1) to 73.4 kg of polycarbonate 2100, 0.4 kg of antioxidant and 0.2 kg of lubricant PETS in a high-speed mixer and mix for 30 min at 30°C and 80 r / min to obtain a premix.

[0117] (3) Add the premix to the twin-screw extruder, and at the same time add 10 kg of glass fiber (ECS13-4.5-510H) to the extruder using a side feeder. Control the temperature of the conveying section of the twin-screw extruder to 260°C, the temperature of the plasticizing section to 280°C, and the temperature of the metering section to 290°C. Control the screw speed to 300 rpm. Control the vacuum device of the metering section of the twin-screw extruder to -0.9 bar to -0.5 bar. After extrusion, drawing, water cooling, air drying, pelletizing, and drying, the blended granules of the flame-retardant high-modulus polycarbonate composition can be obtained.

[0118] Comparative Example 1

[0119] Referring to the method of Example 3, the only difference is that hyperbranched flame retardant compatibilizer and glass fiber are not added in steps (1) and (3) at the same time. Other raw materials and operations are the same as in Example 3, and the polycarbonate composition blend granules are obtained.

[0120] Comparative Example 2

[0121] Referring to the method of Example 3, the only difference is that glass fiber is not added in step (3), while the other raw materials and operations are the same as in Example 3, and the polycarbonate composition blend granules are obtained.

[0122] Comparative Example 3

[0123] Referring to the method of Example 3, the only difference is that hyperbranched flame retardant compatibilizer is not added in steps (1) and (3) at the same time. Other raw materials and operations are the same as in Example 3, and polycarbonate composition blend granules are obtained.

[0124] Comparative Example 4

[0125] Referring to the method of Example 3, the only difference is that in step (1), a conventional compatibilizer, styrene-maleic anhydride copolymer, is added instead of the hyperbranched flame retardant compatibilizer. Other raw materials and operations are the same as in Example 3, and a blend of polycarbonate composition granules is obtained.

[0126] The component content of Examples 1-9 and Comparative Examples 1-4, and the performance tests of the polycarbonate composition blend granules obtained therefrom are shown in the table below:

[0127]

[0128]

[0129] The data in the table shows that hyperbranched compatibilizers containing flame-retardant elements can simultaneously improve the flame-retardant and mechanical properties of glass fiber reinforced PC materials. Furthermore, the addition of hyperbranched flame-retardant compatibilizers can effectively improve the processing flowability of glass fiber reinforced PC.

[0130] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A hyperbranched flame retardant compatibilizer, characterized in that, It has the structure of formula (I): Equation (I).

2. A method for preparing the hyperbranched flame retardant compatibilizer according to claim 1, characterized in that, Includes the following steps: (1) Dissolve 8-12 parts by weight of styrene, 1-5 parts by weight of azobisisobutyronitrile and 2-8 parts by weight of p-vinylbenzylthiol in 60-80 parts by weight of aromatic hydrocarbon to prepare a mixed solution of monomer and initiator. (2) Add 3-6 parts by mass of maleic anhydride, 1-2 parts by mass of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 3-5 parts by mass of p-aminobenzenesulfonic acid and 50-70 parts by mass of aromatic hydrocarbon to a four-necked flask. After complete dissolution, slowly add the mixed solution from step (1) while stirring. Finally, the reaction yields a hyperbranched flame retardant compatibilizer.

3. The preparation method according to claim 2, characterized in that, In step (1), the aromatic hydrocarbon is selected from one or a combination of several of benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, and mixed aromatic hydrocarbons; and / or In step (2), the reaction temperature is 70-140℃ and the reaction time is 8-10h.

4. The preparation method according to claim 3, characterized in that, The aromatic hydrocarbon is toluene.

5. The preparation method according to claim 2, characterized in that, In step (2), the sum of the masses of maleic anhydride, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, p-aminobenzenesulfonic acid, and aromatic hydrocarbons is in a mass ratio of 3 to 7:1 to the mixed solution in step (1).

6. A flame-retardant high-modulus polycarbonate, characterized in that, Includes the following components in parts by weight: 70-90 parts polycarbonate; Antioxidant 0.1-0.5 parts; 1-10 parts of hyperbranched flame retardant compatibilizer; Lubricant 0.2-0.5 parts; 5-40 parts glass fiber; The hyperbranched flame retardant compatibilizer is the hyperbranched flame retardant compatibilizer according to claim 1 or the hyperbranched flame retardant compatibilizer prepared by the preparation method according to any one of claims 2 to 5.

7. The flame-retardant high-modulus polycarbonate according to claim 6, characterized in that, The polycarbonate is selected from one or more of aromatic polycarbonates, aliphatic polycarbonates, and aromatic-aliphatic polycarbonates.

8. The flame-retardant high-modulus polycarbonate according to claim 7, characterized in that, The polycarbonate is bisphenol A type polycarbonate.

9. The flame-retardant high-modulus polycarbonate according to claim 7, characterized in that, Under test conditions of 300℃ and a load of 1.2kg, the melt flow index of the polycarbonate was 6–30 cm⁻¹. 3 Between 10 minutes.

10. The flame-retardant high-modulus polycarbonate according to claim 9, characterized in that, Under test conditions of 300℃ and a load of 1.2kg, the melt flow index of the polycarbonate was 6–20 cm⁻¹. 3 Between 10 minutes.

11. The flame-retardant high-modulus polycarbonate according to claim 10, characterized in that, Under test conditions of 300℃ and a load of 1.2kg, the melt flow index of the polycarbonate was 6–10 cm⁻¹. 3 Between 10 minutes.

12. The flame-retardant high-modulus polycarbonate according to any one of claims 6 to 11, characterized in that, The antioxidant is selected from one or a combination of two or more of the following: hindered phenols, phosphites, thioesters, benzofurans, acryloyl-modified phenols, and hydroxylamines; and / or The lubricant is one or a combination of pentaerythritol stearate, bis-stearamide lubricant, or PE wax; and / or The average diameter of the glass fiber is 6–20 μm.

13. The flame-retardant high-modulus polycarbonate according to claim 12, characterized in that, The antioxidant is a mixture of hindered phenolic antioxidants and phosphite antioxidants, wherein the weight ratio of hindered phenolic antioxidants to phosphite antioxidants is 1 / 4 to 1; and / or The lubricant is pentaerythritol stearate; and / or The average diameter of the glass fiber is 10–16 μm.

14. The method for preparing flame-retardant high-modulus polycarbonate according to any one of claims 6 to 13, characterized in that, Includes the following steps: (1) A master powder was obtained by mixing hyperbranched flame retardant compatibilizer with a portion of polycarbonate; (2) Mix the masterbatch from step (1) with the remaining polycarbonate, antioxidant and lubricant to obtain a premix; (3) Add the premix and glass fiber from step (2) to an extruder for extrusion granulation to obtain flame-retardant high-modulus polycarbonate blend granules; The polycarbonate raw material is added in two steps, with the mass ratio of step (1) to step (2) being 1:1 to 30.

15. The method for preparing flame-retardant high-modulus polycarbonate according to claim 14, characterized in that, The polycarbonate raw material is added in two steps, with the mass ratio of step (1) to step (2) being 1:5 to 20.

16. The method for preparing flame-retardant high-modulus polycarbonate according to claim 14, characterized in that, The mixing described in step (2) is carried out at room temperature, with the stirring temperature controlled below 40°C; the stirring speed is 20–100 r / min, and the mixing time is 15–60 min; and / or The extrusion in step (3) uses a twin-screw extruder. The temperature of the extruder's conveying section is 230-280℃, the temperature of the plasticizing section is 250-290℃, the temperature of the metering section is 260-300℃, and the screw speed is controlled at 200-600 rpm.

17. The method for preparing flame-retardant high-modulus polycarbonate according to claim 16, characterized in that, In step (2), the mixing speed is 40-80 r / min and the mixing time is 20-40 min.

18. The use of the flame-retardant high-modulus polycarbonate according to any one of claims 6 to 13 or the flame-retardant high-modulus polycarbonate prepared by the preparation method according to any one of claims 14 to 17 in flame-retardant high-modulus materials.

19. The application according to claim 18, characterized in that, Applications in the field of rail transit.

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