CN112341779A - High CTI halogen-free flame-retardant reinforced polycarbonate and preparation method and application thereof - Google Patents
High CTI halogen-free flame-retardant reinforced polycarbonate and preparation method and application thereof Download PDFInfo
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- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
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- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention provides a high CTI halogen-free flame-retardant reinforced polycarbonate and a preparation method and application thereof. The high CTI halogen-free flame-retardant reinforced polycarbonate comprises the following components in percentage by mass: 60-70% of polycarbonate, 20-30% of glass fiber modified by silane coupling agent, 5-8% of phosphorus flame retardant, 2-8% of nitrogen flame retardant, 2-8% of toughening agent, 0.4-0.6% of stabilizing agent, 0.01-0.5% of antioxidant, 0.5-1% of lubricant and 0.01-1.0% of light shielding agent. The high CTI halogen-free flame-retardant reinforced polycarbonate realizes halogen-free flame retardance of a composite material, has excellent mechanical property and high CTI value, and is more suitable for preparation of engineering plastics in the field of electronic and electric appliances.
Description
Technical Field
The invention belongs to the field of engineering plastics, and particularly relates to polycarbonate, a preparation method and application thereof, in particular to high CTI halogen-free flame-retardant reinforced polycarbonate, and a preparation method and application thereof.
Background
Engineering plastics based on PC (polycarbonate) have good electrical properties and excellent mechanical properties. It is widely applied to automobiles, electric appliances, office equipment, industrial fields and the like. The engineering plastics have unique superiority compared with wood and metal: the halogen-containing flame retardant has the advantages of light weight, strong impact resistance, excellent electrical performance and the disadvantages of no high temperature resistance, flammability and easy release of toxic gas during combustion, although the traditional halogen-containing flame retardant can achieve the flame retardant effect, the halogen-containing smoke dust released during combustion causes great harm to human bodies, and the electrical performance (CTI value) of the flame retardant and other additives can be greatly reduced by adding the flame retardant and other additives.
At present, the commonly adopted flame retardants are still halogen flame retardants such as decabromodiphenyl ether, tetrabromobisphenol A, and bromine-containing carbonate oligomers, and the halogen flame retardants can release a large amount of toxic substances during combustion, so that the personnel escape and the environmental protection are not facilitated, and simultaneously, due to the large using amount of the halogen flame retardants, the impact strength and the electrical property of the PC material can be greatly reduced while the flame retardant property is enhanced, so that the wide application of the flame-retardant PC material is influenced. At present, halogen-free environment-friendly flame retardants become a trend in order to adapt to market development, and meanwhile, the use of the flame retardants cannot influence the performance of the material.
CN110157174A discloses a glass fiber reinforced flame-retardant polycarbonate composite material, a preparation method and an application thereof, wherein the polycarbonate composite material comprises the following components in percentage by mass: 10-80% of polycarbonate resin, 5-80% of organic silicon chemically modified polycarbonate, 1-8% of organic silicon toughening agent, 5-30% of glass fiber, 0.2-2% of organic silicon flame retardant, 0.1-1% of sulfonate flame retardant and 0.4-3% of auxiliary agent. The composite material has excellent low-temperature impact resistance and flame retardance, but the electrical property of the composite material can be greatly reduced by adding the flame retardant and other additives, and the mechanical property of the composite material is poor due to poor interface bonding when the glass fiber and the polycarbonate resin are compounded.
CN110204881A discloses a surface-quality carbon fiber flame-retardant reinforced polycarbonate composite material, which comprises polycarbonate, surface-active-treated chopped carbon fibers, a toughening agent, a phosphorus flame retardant, a high-phosphorus-content phosphorus-nitrogen flame retardant, a hyperbranched polymer and an additive, wherein the surface-active-treated carbon fibers are matched with the hyperbranched polymer to interact with each other, so that the composite material with the carbon fibers uniformly dispersed in the polycarbonate can be prepared.
Therefore, it is very important to research an environment-friendly, flame-retardant and high CTI polycarbonate.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide polycarbonate and a preparation method and application thereof, in particular to high CTI halogen-free flame-retardant reinforced polycarbonate and a preparation method and application thereof. The high CTI means that the CTI value of the polycarbonate is above 420V. The high CTI halogen-free flame-retardant reinforced polycarbonate realizes halogen-free flame retardance of the composite material, has a high CTI value, is far higher than the requirement of unattended electronic devices (CTI is more than or equal to 300V) provided by IEC organization, and is more suitable for the field of electronic and electric appliances.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a high CTI halogen-free flame-retardant reinforced polycarbonate, which comprises the following components in percentage by mass:
according to the invention, the components of the halogen-free flame-retardant reinforced polycarbonate are matched with each other in a proper proportion, have a synergistic effect, have a high CTI value, and have excellent tensile strength, bending modulus, notch impact strength, thermal deformation temperature and melt index, and the efficient halogen-free flame retardance of the composite material is realized.
The silane coupling agent modified glass fiber can effectively increase the interface strength between the glass fiber and the polycarbonate, is beneficial to the interface compatibility of the composite material, and endows the material with good mechanical strength and higher thermal deformation temperature, thereby improving the reinforcing effect of the glass fiber on the polycarbonate. According to the invention, the phosphorus flame retardant and the nitrogen flame retardant system are compounded, and the non-combustible gas generated by the nitrogen flame retardant and the carbonized layer generated by the phosphorus flame retardant generate a synergistic effect, so that the high-efficiency halogen-free flame retardant of the composite material is realized, and the electrical performance of the polycarbonate is not influenced.
The polycarbonate content is 60-70% by mass of 100% by mass of the high CTI halogen-free flame retardant reinforced polycarbonate, and may be, for example, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70% or the like.
The content of the silane coupling agent modified glass fiber is 20-30% based on 100% of the high CTI halogen-free flame retardant reinforced polycarbonate, and can be, for example, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% and the like.
The phosphorus-based flame retardant content is 5 to 8% by mass of the high CTI halogen-free flame-retardant reinforced polycarbonate being 100%, and may be, for example, 5%, 5.2%, 5.4%, 5.6%, 5.8%, 6%, 6.2%, 6.4%, 6.6%, 6.8%, 7%, 7.2%, 7.4%, 7.6%, 7.8%, 8% or the like.
The content of the nitrogen-based flame retardant is 2 to 8% by mass of the high CTI halogen-free flame-retardant reinforced polycarbonate being 100%, and may be, for example, 2%, 2.5%, 3%, 3.5%, 4%, 4.55%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, etc.
The content of the toughening agent is 2-8% based on 100% of the high CTI halogen-free flame retardant reinforced polycarbonate, and can be, for example, 2%, 2.5%, 3%, 3.5%, 4%, 4.55%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, and the like.
The content of the stabilizer is 0.4-0.6% by mass of the high CTI halogen-free flame retardant reinforced polycarbonate as 100%, and can be 0.4%, 0.45%, 0.5%, 0.55%, 0.6% and the like, for example.
The antioxidant content is 0.1-0.5%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, etc., based on 100% by mass of the high CTI halogen-free flame retardant reinforced polycarbonate.
The content of the lubricant is 0.5-1.0% by mass of 100% of the high CTI halogen-free flame retardant reinforced polycarbonate, and may be, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% or the like.
The light-shielding agent content is 0.1-1.0%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, etc., based on 100% by mass of the high CTI halogen-free flame-retardant reinforced polycarbonate.
Preferably, the polycarbonate has a melt index of 10 to 30g/10min, for example, 10g/10min, 12g/10min, 14g/10min, 16g/10min, 18g/10min, 20g/10min, 22g/10min, 24g/10min, 26g/10min, 28g/10min, 30g/10min, etc., preferably 22g/10 min.
Preferably, the viscosity average molecular weight of the polycarbonate is 30000-40000Da, such as 30000Da, 31000Da, 32000Da, 33000Da, 34000Da, 35000Da, 36000Da, 37000Da, 38000Da, 39000Da, 40000Da and the like.
Preferably, Letian chemical PC-1220 or Sunghuastailon 301-15.
Preferably, the silane coupling agent modified glass fiber is prepared by the following method: and soaking the glass fiber in a silane coupling agent solution, standing, taking out and drying to obtain the silane coupling agent modified glass fiber.
In the invention, the silane coupling agent is used for modifying the glass fiber, thereby not only improving the dispersibility of the glass fiber in the polycarbonate, but also enhancing the interaction of the glass fiber and the polycarbonate, and also improving the impact toughness and tensile strength of the polycarbonate to a certain extent
Preferably, the mass ratio of the glass fiber to the silane coupling agent solution is (1-3): (7-9), and may be, for example, 1:9, 1.5:8.5, 2:8, 2.5:7.5, 3:7, etc.
Preferably, the silane coupling agent solution is an ethanol aqueous solution of the silane coupling agent.
Preferably, the volume ratio of the silane coupling agent to the ethanol aqueous solution is 1 (50-100), and may be, for example, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, or the like.
Preferably, the silane coupling agent comprises any one of KH-550, KH-560, KH-570 or KH-792 or a combination of at least two thereof.
Preferably, the concentration of the ethanol aqueous solution is 1-10% by volume, and may be, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or the like.
Preferably, the standing time is 0.5 to 2 hours, and may be, for example, 0.5 hour, 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1 hour, 1.2 hour, 1.4 hour, 1.6 hour, 1.8 hour, 2 hours, or the like.
Preferably, the temperature of the drying is 80-120 ℃, for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ and the like.
Preferably, the diameter of the glass fiber modified by the silane coupling agent is 10 to 13 μm, and may be, for example, 10 μm, 10.5 μm, 11 μm, 11.5 μm, 12 μm, 12.5 μm, 13 μm, or the like.
Preferably, the phosphorus-based flame retardant comprises any one of triphenyl phosphate, triisobutyl phosphate, tricresyl phosphate, tolyldiphenyl phosphate or condensed aryl phosphate or a combination of at least two of the foregoing.
Preferably, the condensed aryl phosphate ester comprises a resorcinol condensed aryl phosphate ester and/or a condensed phenyl phosphate ester.
Preferably, the nitrogen-based flame retardant comprises any one of melamine, melamine salt or ammonium polyphosphate or a combination of at least two thereof.
Preferably, the melamine salt comprises any one of or a combination of at least two of melamine cyanurate salt, melamine phosphate salt or melamine polyphosphate salt.
Preferably, the toughening agent comprises any one of or a combination of at least two of acrylate-glycidyl ester-ethylene copolymer having an epoxy functional group, methacrylate-styrene-butadiene rubber-styrene copolymer, ethylene-acrylate copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-ethylene-styrene copolymer, styrene-maleic anhydride copolymer or methyl methacrylate-butadiene-styrene copolymer.
Preferably, the toughening agent is a combination of a styrene-maleic anhydride copolymer and a methyl methacrylate-butadiene-styrene copolymer, and the mass ratio of the styrene-maleic anhydride copolymer to the methyl methacrylate-butadiene-styrene copolymer is (1-5: 1, and can be, for example, 1:1, 2:1, 3:1, 4:1, 5:1, and the like.
As a preferable technical scheme of the invention, the toughening agent is prepared by matching styrene-maleic anhydride copolymer (SMA) and methyl methacrylate-butadiene-styrene copolymer (MBS), the styrene-maleic anhydride copolymer (SMA) and the methyl methacrylate-butadiene-styrene copolymer (MBS) are matched with each other to realize synergistic interaction, and under a specific proportion, the tensile strength, the bending modulus and the notch impact strength of the high CTI halogen-free flame retardant reinforced polycarbonate can be further improved.
Preferably, it is characterized in that the stabilizer is dibutyltin dilaurate.
Preferably, the antioxidant comprises antioxidant 1010 and/or antioxidant 1076.
Preferably, the antioxidant is antioxidant 1010 and antioxidant 1076, the mass ratio of the antioxidant 1010 to the antioxidant 1076 is (1-3) to 1, such as 1:1, 2:1, 3:1 and the like,
as a preferred technical scheme of the invention, the antioxidant is used by matching the antioxidant 1010 and the antioxidant 1076, and the matching has a synergistic effect, the antioxidant 1010 can effectively capture oxidation free radicals or peroxide free radicals, and the antioxidant 1076 can supply hydrogen atoms to regenerate the antioxidant 1010 so as to keep the long-term antioxidant effect, thereby generating the synergistic effect.
Preferably, the lubricant comprises any one of a fatty acid amide type lubricant, a fatty acid ester type lubricant, a metal soap type lubricant, a paraffin type lubricant or an organosiloxane type lubricant or a combination of at least two thereof, preferably a fatty acid amide type lubricant.
Preferably, the light-shielding agent is modified titanium dioxide.
The electronic structure of the titanium dioxide is characterized in that a full valence band and an empty conduction band exist, a forbidden band exists between the valence band and the conduction band, and when the nano particles absorb light radiation exceeding band gap energy, the nano oxide is excited from a ground state to an excited state. During this process, an electron jumps from the valence band to the conduction band, forming a positively charged hole in the valence band. The lifetime of the electrons and holes is very short, so that most of the electrons and holes recombine to release heat during the migration process. Through the process, light energy is converted into heat energy, the function of the ultraviolet absorbent is embodied, and meanwhile, the ultraviolet absorbent is not consumed, so that the titanium dioxide can embody a superior ultraviolet shielding effect in a long time span.
Preferably, the particle diameter of the modified titanium dioxide is 20-22nm, for example, 20nm, 20.5nm, 21nm, 21.5nm, 22nm and the like, and the specific surface area of the modified titanium dioxide is 35-65m2Per g, may be, for example, 35m2/g、40m2/g、45m2/g、50m2/g、55m2/g、60m2/g、65m2And/g, etc.
Preferably, the modified titanium dioxide is fumed titanium dioxide AEROXIDE P25 of degussa, germany; belonging to mixed crystal type, the weight ratio of anatase to rutile is about 80/20, and TiO is enlarged due to the mixing of the two structures2The defect density in the crystal lattice increases the concentration of current carriers, increases the quantity of electrons and holes and has stronger trapping in TiO2Capacity of the solution components (water, oxygen, organic) of the surface.
In a second aspect, the present invention provides a method for preparing the high CTI halogen-free flame retardant reinforced polycarbonate according to the first aspect, the method comprises the following steps:
(1) mixing polycarbonate, silane coupling agent modified glass fiber, phosphorus flame retardant, nitrogen flame retardant, toughening agent, stabilizer, antioxidant, lubricant and light shielding agent to obtain a mixture;
(2) and (2) carrying out melting mixing and extrusion granulation on the mixture obtained in the step (1) to obtain the high CTI halogen-free flame retardant reinforced polycarbonate.
Preferably, the polycarbonate needs to be dried in step (1) before mixing, the drying temperature is 110-130 ℃, for example, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃ and the like, and the drying time is 3-4h, for example, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h and the like.
Preferably, the mixing in step (1) is performed in a high speed mixer, and the rotation speed of the mixing is 1000-1200rpm, such as 1000rpm, 1050rpm, 1100rpm, 1150rpm, 1200rpm, etc.
Preferably, the melt-kneading and extrusion-pelletization in the step (2) are carried out in a twin-screw extruder.
Preferably, the twin screw extruder has a length to diameter ratio of 32 or greater, and can be, for example, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, and the like.
Preferably, the temperature of the melt kneading in the step (2) is 240-260 ℃, and may be, for example, 240 ℃, 245 ℃, 250 ℃, 255 ℃, 260 ℃ or the like.
Preferably, after the extrusion granulation in the step (2), pulling and drawing, water tank cooling, dehydration and granulation are sequentially performed.
Preferably, the preparation method of the high CTI halogen-free flame retardant reinforced polycarbonate comprises the following steps:
(1) drying the polycarbonate at the temperature of 110-;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder with the length-diameter ratio not less than 32, and carrying out melt mixing and extrusion granulation at the temperature of 240-260 ℃ to obtain the high CTI halogen-free flame-retardant reinforced polycarbonate.
In a third aspect, the invention provides an application of the high CTI halogen-free flame retardant reinforced polycarbonate in preparing engineering plastics.
The high CTI halogen-free flame-retardant reinforced polycarbonate has a CTI value of more than 420V, so that the high CTI halogen-free flame-retardant reinforced polycarbonate is suitable for preparing engineering plastics in the field of electronic and electric appliances, such as sockets, chargers, connectors, industrial lighting, electronic products, electric appliance shells and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) the silane coupling agent modified glass fiber can effectively increase the interface strength between the glass fiber and the polycarbonate, and is beneficial to the interface compatibility of composite materials, so that the reinforcing effect of the glass fiber on the polycarbonate is improved. According to the invention, the phosphorus flame retardant and the nitrogen flame retardant system are compounded, and the non-combustible gas generated by the nitrogen flame retardant and the carbonized layer generated by the phosphorus flame retardant generate a synergistic effect, so that the high-efficiency halogen-free flame retardant of the composite material is realized, and the electrical performance of the polycarbonate is not influenced.
(2) The high CTI halogen-free flame-retardant reinforced polycarbonate provided by the invention has the tensile strength of 95-105MPa, the bending strength of 155-170MPa, the bending modulus of 10000-12500MPa and the notch impact strength of 110-125kJ/m2Thermal change ofThe forming temperature is 95-100 ℃, the melt index is 17-19g/10min, the flame retardant performance can reach V0 grade when all the flame retardant performance are 1.6mm, and the CTI value is 425-450V.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The sources of the components in the following examples are as follows: polycarbonate (manufacturer: Letian, brand: PC1220), resorcinol condensed aryl phosphate (manufacturer: cappuccino, brand: RDP), melamine cyanurate (manufacturer: Protak, Melamine cyanurate (manufacturer: Protak, Melamine, modified titanium dioxide (manufacturer: Yingchuangdegusai gas-phase titanium dioxide, brand: AEROXIDE P25), unmodified titanium dioxide (manufacturer: Shandong Jia, brand: SR-2377), and unmodified glass fiber (manufacturer: Hangzhou Gaokouke, brand: ECP).
The silane coupling agent modified glass fibers provided in the following examples were prepared by the following method: mixing KH-550 with 60 wt% ethanol aqueous solution at a volume ratio of 1:50 to obtain KH-550 ethanol aqueous solution; soaking the glass fiber in 60 wt% ethanol water solution of KH-550, wherein the mass ratio of the glass fiber to the silane coupling agent solution is 2:8, standing for 1h, taking out, and drying at 100 ℃ to obtain the modified glass fiber with the particle size of 12 microns.
Example 1
The embodiment provides a high CTI halogen-free flame-retardant reinforced polycarbonate, which comprises the following components in percentage by mass:
the preparation method of the high CTI halogen-free flame-retardant reinforced polycarbonate comprises the following steps:
(1) drying polycarbonate at 120 ℃ for 3.5h, and then mixing the polycarbonate, the glass fiber modified by the silane coupling agent, the phosphorus flame retardant, the nitrogen flame retardant, the toughening agent, the stabilizer, the antioxidant, the lubricant and the light shielding agent in a high-speed mixer at the rotating speed of 1100rpm to obtain a mixture;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder with the length-diameter ratio of 40, carrying out melting mixing and extrusion granulation at 250 ℃, and then sequentially carrying out pulling strip, water tank cooling, dehydration and grain cutting to obtain the high CTI halogen-free flame retardant reinforced polycarbonate.
Example 2
The embodiment provides a high CTI halogen-free flame-retardant reinforced polycarbonate, which comprises the following components in percentage by mass:
the preparation method of the high CTI halogen-free flame-retardant reinforced polycarbonate comprises the following steps:
(1) drying polycarbonate at 110 ℃ for 4h, and then mixing the polycarbonate, the glass fiber modified by the silane coupling agent, the phosphorus flame retardant, the nitrogen flame retardant, the toughening agent, the stabilizer, the antioxidant, the lubricant and the light shielding agent in a high-speed mixer at the rotating speed of 1200rpm to obtain a mixture;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder with the length-diameter ratio of 40, carrying out melting mixing and extrusion granulation at 240 ℃, and then sequentially carrying out pulling strip, water tank cooling, dehydration and grain cutting to obtain the high CTI halogen-free flame retardant reinforced polycarbonate.
Example 3
The embodiment provides a high CTI halogen-free flame-retardant reinforced polycarbonate, which comprises the following components in percentage by mass:
the preparation method of the high CTI halogen-free flame-retardant reinforced polycarbonate comprises the following steps:
(1) drying polycarbonate at 120 ℃ for 3h, and then mixing the polycarbonate, the glass fiber modified by the silane coupling agent, the phosphorus flame retardant, the nitrogen flame retardant, the toughening agent, the stabilizer, the antioxidant, the lubricant and the light shielding agent in a high-speed mixer at the rotating speed of 1000rpm to obtain a mixture;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder with the length-diameter ratio of 40, carrying out melting mixing and extrusion granulation at 260 ℃, and then sequentially carrying out pulling strip, water tank cooling, dehydration and grain cutting to obtain the high CTI halogen-free flame retardant reinforced polycarbonate.
Example 4
This example provides a high CTI halogen-free flame retardant reinforced polycarbonate, which is different from example 1 only in that no styrene-maleic anhydride copolymer is added to the toughening agent, the content of the methyl methacrylate-butadiene-styrene copolymer is increased to 5%, and the content of other components and the preparation method are the same as example 1.
Example 5
This example provides a high CTI halogen-free flame retardant reinforced polycarbonate, which is different from example 1 only in that the toughening agent is not added with a methyl methacrylate-butadiene-styrene copolymer, the content of the styrene-maleic anhydride copolymer is increased to 5%, and the content of other components and the preparation method are the same as example 1.
Example 6
This example provides a high CTI halogen-free flame retardant reinforced polycarbonate, which is different from example 1 only in that the content of the styrene-maleic anhydride copolymer is reduced to 0.5%, the content of the methyl methacrylate-butadiene-styrene copolymer is increased to 4.5%, and the content of other components and the preparation method are the same as example 1.
Example 7
This example provides a high CTI halogen-free flame retardant reinforced polycarbonate, which is different from example 1 only in that the content of the styrene-maleic anhydride copolymer is reduced to 4.5%, the content of the methyl methacrylate-butadiene-styrene copolymer is increased to 0.5%, and the content of other components and the preparation method are the same as example 1.
Example 8
The embodiment provides a high CTI halogen-free flame retardant reinforced polycarbonate, which is different from the embodiment 1 only in that the antioxidant is not added with the antioxidant 1010, the content of the antioxidant 1076 is increased to 0.3%, and the content of other components and the preparation method are the same as the embodiment 1.
Example 9
The embodiment provides a high CTI halogen-free flame retardant reinforced polycarbonate, which is different from the embodiment 1 only in that the antioxidant is not added with the antioxidant 1076, the content of the antioxidant 1010 is increased to 0.3%, and the content of other components and the preparation method are the same as the embodiment 1.
Example 10
The embodiment provides a high CTI halogen-free flame retardant reinforced polycarbonate, which is different from the embodiment 1 only in that the content of the antioxidant 1010 is reduced to 0.05%, the content of the antioxidant 1076 is increased to 0.25%, and the content of other components and the preparation method are the same as the embodiment 1.
Example 11
The embodiment provides a high CTI halogen-free flame retardant reinforced polycarbonate, which is different from the embodiment 1 only in that the content of the antioxidant 1010 is reduced to 0.25%, the content of the antioxidant 1076 is increased to 0.05%, and the content of other components and the preparation method are the same as the embodiment 1.
Example 12
The embodiment provides a high CTI halogen-free flame retardant reinforced polycarbonate, which is different from the embodiment 1 only in that the fatty acid amide lubricant is replaced by the fatty acid ester lubricant, and the contents of other components and the preparation method are the same as the embodiment 1.
Example 13
The embodiment provides a high CTI halogen-free flame retardant reinforced polycarbonate, which is different from the embodiment 1 only in that the modified titanium dioxide is replaced by unmodified titanium dioxide, and the contents of other components and the preparation method are the same as the embodiment 1.
Comparative example 1
The comparative example provides a reinforced polycarbonate, and is different from the reinforced polycarbonate in example 1 only in that the high CTI halogen-free flame retardant reinforced polycarbonate is not added with a phosphorus flame retardant and a nitrogen flame retardant, the content of the polycarbonate is increased to 73.5%, and the content of other components and the preparation method are the same as those of example 1.
Comparative example 2
The comparative example provides a reinforced polycarbonate, and is different from the reinforced polycarbonate in example 1 only in that the high CTI halogen-free flame retardant reinforced polycarbonate is not added with a phosphorus flame retardant, a nitrogen flame retardant and a toughening agent, the content of the polycarbonate is increased to 78.5%, and the content of other components and the preparation method are the same as those in example 1.
Comparative example 3
The comparative example provides a reinforced polycarbonate, and is different from the reinforced polycarbonate in example 1 only in that no toughening agent is added to the high CTI halogen-free flame retardant reinforced polycarbonate, the content of the polycarbonate is increased to 65.5%, and the content of other components and the preparation method are the same as those of example 1.
Comparative example 4
The comparative example provides a reinforced polycarbonate, which is different from the polycarbonate in the example 1 only in that a phosphorus flame retardant (condensed phenyl phosphate) is not added into the high CTI halogen-free flame retardant reinforced polycarbonate, the content of a nitrogen flame retardant (phosphate melamine salt) is increased to 13 percent, and the content of other components and the preparation method are the same as those of the polycarbonate in the example 1.
Comparative example 5
The comparative example provides a reinforced polycarbonate, which is different from the polycarbonate in the example 1 only in that a nitrogen-based flame retardant (melamine phosphate) is not added into the high CTI halogen-free flame-retardant reinforced polycarbonate, the content of a phosphorus-based flame retardant (condensed phenyl phosphate) is increased to 13 percent, and the content of other components and the preparation method are the same as those of the polycarbonate in the example 1.
Comparative example 6
This comparative example provides a reinforced polycarbonate, which is different from example 1 only in that the content of the phosphorus-based flame retardant (condensed phenyl phosphate) is increased to 10%, the content of the nitrogen-based flame retardant (melamine phosphate) is reduced to 3%, and the contents of other components and the preparation method are the same as example 1.
Comparative example 7
This comparative example provides a reinforced polycarbonate, which is different from example 1 only in that the content of the phosphorus-based flame retardant (condensed phenyl phosphate) is reduced to 3%, the content of the nitrogen-based flame retardant (melamine phosphate) is increased to 10%, and the contents of other components and the preparation method are the same as example 1.
Comparative example 8
This comparative example provides a reinforced polycarbonate, which is different from example 1 only in that the glass fiber modified with a silane coupling agent is replaced with the unmodified glass fiber, and the contents of other components and the preparation method are the same as those of example 1.
Performance testing
The high CTI halogen-free flame retardant reinforced polycarbonate provided by the embodiments 1 to 13 and the reinforced polycarbonate provided by the comparative examples 1 to 8 are subjected to various performance tests, including tensile strength, bending modulus, notch impact strength, heat distortion temperature, melt index, combustion performance and CTI value of the material;
specific test criteria and results are shown in table 1:
TABLE 1
As shown in the test data in Table 1, the high CTI halogen-free flame retardant reinforced polycarbonate provided by the invention has the tensile strength of 95-105MPa, the bending strength of 155-12500 MPa, the bending modulus of 10000-12500MPa and the notched impact strength of 110-125kJ/m2The heat distortion temperature is 95-100 ℃, the melt index is 17-19g/10min, the flame retardant performance can reach V0 grade when all the flame retardant performances are 1.6mm, and the CTI value is 425-450V. The halogen-free flame-retardant reinforced polycarbonate with high CTI provided by the invention realizes halogen-free flame retardance of the composite material, has excellent mechanical properties and high CTI value, and is more suitable for preparation of engineering plastics in the field of electronic and electric appliances.
As can be seen from the comparison between example 1 and comparative example 1, the polycarbonate does not contain phosphorus flame retardants and nitrogen flame retardants, so that not only is the flame retardant performance obviously reduced, but also the CTI of the material is obviously reduced, the heat deformation temperature is reduced, and the mechanical properties of the polycarbonate are also obviously reduced. As can be seen from the comparison between example 1 and comparative example 3, the mechanical properties of the material are obviously reduced without adding a toughening agent into the polycarbonate.
As can be seen from the comparison between the example 1 and the comparative examples 4 and 5, the example 1 adopts the combination of the phosphorus flame retardant and the nitrogen flame retardant system, and the non-combustible gas generated by the nitrogen flame retardant and the carbonized layer generated by the phosphorus flame retardant generate a synergistic effect, so that the halogen-free flame retardance of the composite material can be efficiently realized, and the CTI value is obviously improved. As can be seen from the comparison between example 1 and comparative examples 6 and 7, the phosphorus flame retardant and the nitrogen flame retardant can exert the synergistic flame retardant effect of phosphorus and nitrogen elements at a certain ratio, thereby improving the flame retardant effect on the high polymer material and reducing the use amount of the flame retardant in the high polymer material.
It can be seen from the comparison between example 1 and comparative example 8 that the mechanical properties of the glass fiber modified by the silane coupling agent are significantly reduced after the glass fiber is replaced by the unmodified glass fiber, because the unmodified glass fiber has poor interface compatibility with the polycarbonate and low interface bonding strength, and the glass fiber cannot sufficiently exert the reinforcing effect on the polycarbonate.
The applicant states that the present invention is illustrated by the above examples to show the high CTI halogen-free flame retardant reinforced polycarbonate, the preparation method and the application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The high CTI halogen-free flame-retardant reinforced polycarbonate is characterized by comprising the following components in percentage by mass:
2. the high CTI halogen free flame retardant reinforced polycarbonate of claim 1, wherein the polycarbonate has a melt index of 10 to 30g/10min, preferably 22g/10 min;
preferably, the viscosity average molecular weight of the polycarbonate is 30000-40000 Da.
3. The high CTI halogen-free flame retardant reinforced polycarbonate of claim 1 or 2, wherein the silane coupling agent modified glass fiber is prepared by the following method: soaking glass fiber in a silane coupling agent solution, standing, taking out and drying to obtain the silane coupling agent modified glass fiber;
preferably, the mass ratio of the glass fiber to the silane coupling agent solution is (1-3) to (7-9);
preferably, the silane coupling agent solution is an ethanol aqueous solution of a silane coupling agent;
preferably, the volume ratio of the silane coupling agent to the ethanol aqueous solution is 1 (50-100);
preferably, the silane coupling agent comprises any one of KH-550, KH-560, KH-570 or KH-792 or a combination of at least two thereof;
preferably, the standing time is 0.5-2 h;
preferably, the drying temperature is 80-120 ℃;
preferably, the diameter of the glass fiber modified by the silane coupling agent is 10 to 13 μm.
4. The high CTI halogen free flame retardant reinforced polycarbonate of any of claims 1-3, wherein the phosphorus based flame retardant comprises any one or a combination of at least two of triphenyl phosphate, triisobutyl phosphate, tricresyl phosphate, tolyldiphenyl phosphate, or condensed aryl phosphate;
preferably, the condensed aryl phosphate ester comprises resorcinol condensed aryl phosphate ester and/or condensed phenyl phosphate;
preferably, the nitrogen-based flame retardant comprises any one of melamine, melamine salt or ammonium polyphosphate or a combination of at least two of the same;
preferably, the melamine salt comprises any one of or a combination of at least two of melamine cyanurate salt, melamine phosphate salt or melamine polyphosphate salt.
5. The high CTI halogen free flame retardant reinforced polycarbonate of any of claims 1 to 4, wherein the toughening agent comprises any one of or a combination of at least two of acrylate-glycidyl ester-ethylene copolymer with epoxy functional groups, methacrylate-styrene butadiene rubber-styrene copolymer, ethylene-acrylate copolymer, ethylene vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-ethylene-styrene copolymer, styrene-maleic anhydride copolymer, or methyl methacrylate-butadiene-styrene copolymer;
preferably, the toughening agent is a combination of a styrene-maleic anhydride copolymer and a methyl methacrylate-butadiene-styrene copolymer, and the mass ratio of the styrene-maleic anhydride copolymer to the methyl methacrylate-butadiene-styrene copolymer is (1-5): 1.
6. The high CTI, halogen free, flame retardant reinforced polycarbonate of any of claims 1-5, wherein the stabilizer is dibutyltin dilaurate;
preferably, the antioxidant comprises antioxidant 1010 and/or antioxidant 1076;
preferably, the antioxidant is an antioxidant 1010 and an antioxidant 1076, and the mass ratio of the antioxidant 1010 to the antioxidant 1076 is (1-3) to 1;
preferably, the lubricant comprises any one of a fatty acid amide type lubricant, a fatty acid ester type lubricant, a metal soap type lubricant, a paraffin type lubricant or an organosiloxane type lubricant or a combination of at least two of them, preferably a fatty acid amide type lubricant;
preferably, the light-shielding agent is modified titanium dioxide;
preferably, the particle size of the modified titanium dioxide is 20-22nm, and the specific surface area of the modified titanium dioxide is 35-65m2/g。
7. The preparation method of the high CTI halogen-free flame retardant reinforced polycarbonate according to any one of claims 1 to 6, characterized by comprising the following steps:
(1) mixing polycarbonate, silane coupling agent modified glass fiber, phosphorus flame retardant, nitrogen flame retardant, toughening agent, stabilizer, antioxidant, lubricant and light shielding agent to obtain a mixture;
(2) and (2) carrying out melting mixing and extrusion granulation on the mixture obtained in the step (1) to obtain the high CTI halogen-free flame retardant reinforced polycarbonate.
8. The method according to claim 7, wherein the polycarbonate in step (1) is dried before mixing, the drying temperature is 110 ℃ to 130 ℃, and the drying time is 3-4 h;
preferably, the mixing in step (1) is carried out in a high-speed mixer, and the rotation speed of the mixing is 1000-;
preferably, the melt mixing and the extrusion granulation in the step (2) are both carried out in a double-screw extruder;
preferably, the length-diameter ratio of the double-screw extruder is more than or equal to 32;
preferably, the temperature for melting and mixing in the step (2) is 240-260 ℃;
preferably, after the extrusion granulation in the step (2), pulling and drawing, water tank cooling, dehydration and granulation are sequentially performed.
9. The preparation method of claim 7 or 8, wherein the preparation method of the high CTI halogen-free flame retardant reinforced polycarbonate comprises the following steps:
(1) drying the polycarbonate at the temperature of 110-;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder with the length-diameter ratio not less than 32, carrying out melt mixing and extrusion granulation at the temperature of 240-260 ℃, and then sequentially carrying out traction bracing, water tank cooling, dehydration and grain cutting to obtain the high CTI halogen-free flame retardant reinforced polycarbonate.
10. Use of the high CTI halogen free flame retardant reinforced polycarbonate of any of claims 1-6 in the preparation of engineering plastics.
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Application publication date: 20210209 |