CN114149673B - High CTI halogen-free flame-retardant polycarbonate material and preparation process thereof - Google Patents

High CTI halogen-free flame-retardant polycarbonate material and preparation process thereof Download PDF

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CN114149673B
CN114149673B CN202111526934.5A CN202111526934A CN114149673B CN 114149673 B CN114149673 B CN 114149673B CN 202111526934 A CN202111526934 A CN 202111526934A CN 114149673 B CN114149673 B CN 114149673B
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flame retardant
polycarbonate
silane coupling
antioxidant
coupling agent
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CN114149673A (en
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林建民
蔡鹏飞
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Fujian Huasu Innovative Plastics Material Co ltd
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
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Abstract

The invention provides a high CTI halogen-free flame retardant polycarbonate material which is characterized by comprising the following components in parts by weight: 60-80 parts of polycarbonate, 10-30 parts of modified reinforcing agent, 5-10 parts of flame retardant, 3-8 parts of toughening agent, 0.1-1 part of antioxidant and 0.1-1 part of lubricant. The modifying and reinforcing agent is silane coupling agent modified glass fiber and/or silane coupling agent modified mineral filler, and the fire retardant is microcapsule fire retardant prepared by coating capsule core with capsule wall. The polycarbonate material prepared by the invention has CTI value of more than 420V, good flame retardant effect and good mechanical property, and can be applied to the field of electronic and electric appliances.

Description

High CTI halogen-free flame-retardant polycarbonate material and preparation process thereof
Technical Field
The invention belongs to the technical field of engineering plastic/polymer modification processing, and particularly relates to a high CTI halogen-free flame-retardant glass fiber reinforced polycarbonate material and a preparation process thereof.
Background
Along with the rapid development of the electronic and electrical appliance industry in China and the improvement of the living standard of people, people pay more and more attention to the use performance and the safety performance of electronic and electrical appliance products, so that the appearance is attractive, the performance is excellent, and the use safety of household appliances is required to be higher. For an unattended white household appliance, the flame retardant property and the higher electrical property are required, the Comparative Tracking Index (CTI) is required to be more than or equal to 300V, and the requirement is higher and higher along with the development of material modification.
The Polycarbonate (PC) material has excellent mechanical property, dimensional stability and thermal property, and is widely applied in the field of electric appliance manufacture. Electronic devices such as connectors, transformers, fuse housings, switches, relays, energy saving lamps, coil bobbins, connectors, etc. may all be manufactured using polycarbonate. Typically, electronic devices can cause localized overheating and can cause combustion in the event of an overload, short circuit, electrical leakage, and the like. Therefore, the electronic device manufacturing field usually has very strict flame retardant requirements on materials, and generally requires that the whole-course non-ignition temperature of a glow wire reaches 750 ℃. In order to meet the flame retardant requirement of the material, the industry selects to add a flame retardant, but the flame retardant can reduce the mechanical properties of the material. In addition, the flame retardant can also affect the electrical insulation performance of the material, for example, the CTI of the material is reduced from 600V to 250V or even lower by adding a large amount of the flame retardant, which directly affects the application of the material in the field of electronic and electric appliances.
Patent document 201910363726.4 discloses a halogen-free flame-retardant glass fiber mineral reinforced high CTI polycarbonate, which comprises main materials and auxiliary materials, and is characterized in that: the main material comprises a reinforced carrier, a light-transmitting carrier and polycarbonate, and the auxiliary material comprises a flame-retardant carrier, a toughening agent, an electrostatic preventing agent, an ultraviolet absorbent, a lubricant, an anti-dripping agent and an antioxidant. The reinforcing carrier is mineral filling, the mineral filling is mixed mineral of graphite, mica and porous carbon, and the ratio of the graphite to the mica to the porous carbon is 3:4: 1. The light-transmitting carrier is a mixed solution of glass fiber, xylene and cedar oil, wherein the ratio of the glass fiber to the xylene to the cedar oil is 4:2: 1. The improvement point of the technical scheme is that the graphite and the mica are added into the polycarbonate, so that the strength, the wear resistance and other properties of the product can be enhanced, the shock resistance of the product is improved, and the product has enough toughness. Although the strength of the material can be improved by adding mineral fillers into polycarbonate, the interfacial adhesion between the mineral and the polycarbonate is not good, and the mechanical properties of the material, such as tensile property and the like, can be affected.
Patent document 202011131801.3 discloses a high CTI halogen-free flame retardant reinforced polycarbonate, which 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. Although the technical scheme realizes halogen-free flame retardance of the composite material, has excellent CTI value and is suitable for preparation of engineering plastics in the field of electronics, a large amount of flame retardant is directly added into the system, and the mechanical property of the material is influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polycarbonate material, a preparation method and application thereof, wherein the polycarbonate material realizes the performance of high CTI under the halogen-free flame-retardant condition. The high CTI means that the CTI value of the polycarbonate material is more than 420V and is far higher than the requirement of unattended electronic devices (the CTI is more than or equal to 300V) provided by IEC organization, and the polycarbonate material is more suitable for the field of electronic and electric appliances.
The purpose of the invention is realized by the following technical scheme.
In a first aspect, the invention provides a high CTI halogen-free flame retardant polycarbonate material, which is characterized by comprising the following components in parts by weight: 60-80 parts of polycarbonate, 10-30 parts of modified reinforcing agent, 5-10 parts of flame retardant, 3-8 parts of toughening agent, 0.1-1 part of antioxidant and 0.1-1 part of lubricant.
In a preferred embodiment of the invention, the high CTI halogen-free flame retardant polycarbonate material comprises the following components in parts by weight: 70-80 parts of polycarbonate, 15-20 parts of modified reinforcing agent, 5-6 parts of flame retardant, 5-8 parts of toughening agent, 0.1-0.3 part of antioxidant and 0.1-0.5 part of lubricant.
The polycarbonate used in the invention is one or two of aromatic polycarbonate and aliphatic polycarbonate, preferably bisphenol A polycarbonate, and the melt index of the bisphenol A polycarbonate is 15-30g/10 min.
The modification reinforcing agent is glass fiber modified by silane coupling agent and/or mineral filler modified by silane coupling agent. The diameter of the glass fiber is 10-15 μm, and the mineral filler comprises at least one of calcium carbonate whisker, calcium sulfate whisker and silicon carbide whisker.
In the preferred embodiment of the invention, the glass fiber modified by the silane coupling agent and the mineral filler modified by the silane coupling agent are obtained by the conventional method in the field, namely, the glass fiber and/or the mineral filler are soaked in the silane coupling agent solution for 30-60min, and then are taken out and dried, and are uniformly dispersed.
Preferably, the mass ratio of the glass fiber and/or mineral filler to the silane coupling agent solution is 1: (5-7).
Preferably, the silane coupling agent solution is prepared by mixing a silane coupling agent and an ethanol water solution according to the volume ratio of 1 (50-100), wherein the silane coupling agent is selected from one or a combination of more than two of KH-550, KH-560 and KH-570.
The toughening agent is selected from the combination of styrene grafted maleic anhydride and methyl methacrylate-butadiene-styrene copolymer, and the mass ratio is (1-3): 1.
the antioxidant is selected from the compound of antioxidant 1010, antioxidant 1076 and antioxidant 168, and the mass ratio of the antioxidant 1010: antioxidant 1076: antioxidant 168 ═ 1: 1: (1-1.5).
The lubricant is selected from one or more of fatty acid ester lubricant, paraffin lubricant and organic siloxane lubricant.
In a preferred embodiment of the present invention, the lubricant is a combination of pentaerythritol stearate and silicone powder, and the mass ratio is 1: (0.2-0.5).
The flame retardant is a microcapsule flame retardant prepared by coating a capsule core with a capsule wall, the mass ratio of the capsule wall to the capsule core is (0.1-0.4):1, the capsule core is a phosphorus flame retardant, the capsule wall is a cured product of bisphenol A epoxy resin and a curing agent, the bisphenol A epoxy resin is selected from one or a combination of two of E44, E51 and E54, and the epoxy equivalent is 160-190. The curing agent is polyether amine curing agent or polyamide curing agent, and the equivalent weight of active hydrogen of the curing agent is 50-80.
The phosphorus flame retardant comprises one or the combination of more than two of triphenyl phosphate, triisobutyl phosphate and tricresyl phosphate.
Preferably, the capsule wall further comprises an epoxy cage silsesquioxane (epoxy POSS).
More preferably, the capsule wall is a cured product of bisphenol a epoxy resin and epoxy-based POSS reacted with a curing agent, wherein the mass ratio of bisphenol a epoxy resin to epoxy-based POSS is 1: (0.1-0.4).
Preferably, the epoxy POSS is a compound of formula I,
Figure BDA0003409343020000051
r is 2, 3-glycidoxypropyl and 3, 4-epoxycyclohexylethyl.
In a preferred embodiment of the present invention, the epoxy-based POSS structural formula is as follows:
Figure BDA0003409343020000052
r is
Figure BDA0003409343020000053
Cage type octa (2, 3-glycidoxypropyl) POSS
Figure BDA0003409343020000061
R is
Figure BDA0003409343020000062
Cage-type octa (3, 4-epoxycyclohexylethyl) POSS
The fire retardant microcapsule technology is that natural or synthetic polymer material is used to form one layer of inert protecting film on the surface of fire retardant, and the protecting film is destroyed to release the fire retardant to reach fire retarding effect. The inventors have unexpectedly found that the combination of epoxy POSS and bisphenol A epoxy resin is preferably used as the capsule wall material of the microcapsule type flame retardant, so that the capsule wall material not only has better protection effect on the capsule core phosphorus flame retardant, but also can enhance the mechanical properties of the polycarbonate material. Because the molecular formula of the epoxy group POSS is (RSiO) 3/2 ) n The property of which is between that of silicon dioxide (SiO) 2 ) With silicone resin (R) 2 SiO) n A polyhedral inorganic framework core with a Si-O structure, and the periphery of the polyhedral inorganic framework core is surrounded by organic groups. When epoxy group POSS can be reacted with bisphenol A epoxy resinUnder the condition of better lipid compatibility, the two can be cured together, and the POSS compound containing Si-O bonds is mixed in the bisphenol A epoxy resin to ensure that the capsule wall structure of the microcapsule is more stable and a more compact protective film is formed.
The microcapsule type flame retardant is prepared by the following method:
(1) dispersing a phosphorus flame retardant in a solvent under a stirring state to obtain a mixed solution, and adding a bisphenol A epoxy resin and/or an epoxy group POSS solution when the temperature is raised to 35-45 ℃;
(2) weighing a curing agent, dissolving the curing agent in water to obtain a curing agent solution, dropwise adding the curing agent solution into the mixed solution obtained in the step (1), gradually heating to 60-65 ℃, and keeping the reaction for 6-7 hours; and cooling to room temperature, washing and centrifuging until the upper layer liquid is colorless and transparent, drying and dispersing the precipitate, and preparing the microcapsule type flame retardant.
In the step (1), the solvent is one or the combination of two of methanol, absolute ethyl alcohol, butanol and chloroform.
The epoxy resin and/or epoxy group POSS solution in the step (1) is prepared by dissolving the epoxy resin and the epoxy group POSS in solvents such as absolute ethyl alcohol, acetone, chloroform and the like respectively or simultaneously, the dosage of the solvents is not specially limited, and the solvents are preferably used for completely dissolving the bisphenol A epoxy resin and the epoxy group POSS.
In a second aspect, the invention provides a preparation method of a high CTI halogen-free flame retardant polycarbonate material, which comprises the following steps:
(1) drying the polycarbonate at the temperature of 100-;
(2) and (2) adding the mixed material obtained in the step (1) into a double-screw extruder, and performing melt extrusion and granulation to obtain the high CTI halogen-free flame retardant polycarbonate material.
In a third aspect, the invention provides application of a high CTI halogen-free flame-retardant polycarbonate material in preparation of engineering plastics in the field of electronics.
The high CTI halogen-free flame retardant polycarbonate material provided by the invention has the following technical advantages: (1) the glass fiber and the mineral filler modified by the silane coupling agent are used as additives to improve the mechanical property of the polyurethane material. Conventionally, the interface compatibility between the glass fiber and the mineral filler and the polymer material is poor, and the mechanical property of the polymer material can be influenced after the glass fiber and the mineral filler with unmodified surfaces are directly added. The glass fiber and the mineral filler used in the invention are both products modified by silane coupling agent, and the silane coupling agent modification can obviously enhance the interface strength of the inorganic filler and the polycarbonate and enhance the mechanical property of the polycarbonate material.
(2) According to the invention, the flame retardant is added in a microcapsule form, so that the flame retardance of the finally prepared polycarbonate material is improved, and the mechanical properties of the material are obviously improved. As known to those skilled in the art, the phosphorus flame retardant is an inorganic substance with strong polarity, and has poor compatibility with a high polymer material polycarbonate, and the mechanical properties of the material can be seriously affected by direct doping. The inventors of the present invention have unexpectedly found that the phosphorus flame retardant coated with the high molecular polymer can significantly improve the surface polarity of the particles, and improve the compatibility of the flame retardant with polycarbonate materials. The microcapsule type flame retardant prepared by the invention takes epoxy resin and epoxy group POSS as capsule walls, and a layer of protective film is formed on the surface of the phosphorus-containing flame retardant after in-situ polymerization and solidification, so that the protective film not only improves the compatibility of the flame retardant and a polycarbonate material, but also isolates the flame retardant from the external environment, and the flame retardant can play a better role. In addition, the epoxy group POSS also has a certain flame retardant effect, so that the microcapsule type flame retardant prepared by the invention has better thermal stability and obviously improved flame retardant effect compared with a flame retardant only using phosphorus.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials involved in the examples of the present invention are as follows: polycarbonate (melt index 15g/10min), purchased from Sigma-Aldrich, silane coupling agent from Nanjing Youpu chemical, styrene grafted maleic anhydride from German Pasv, methyl methacrylate-butadiene-styrene copolymer from Kabuda chemical, antioxidant 1010, antioxidant 1076, antioxidant 168 from German Pasv, pentaerythritol stearate from Hemicanite, silicone powder from Kejie Polymer.
Preparation example
Silane coupling agent modified glass fiber
Mixing a silane coupling agent KH-550 and 70 wt% of ethanol according to a volume ratio of 1:50 to obtain a silane coupling agent solution; soaking glass fiber (with the diameter of 10-12 mu m, purchased from Hangzhou Gaokou) in a silane coupling agent solution for 60min, taking out the glass fiber and the silane coupling agent solution according to the mass ratio of 1:5, and drying the glass fiber in a drying oven at 100 ℃ to prepare the silane coupling agent modified glass fiber.
Silane coupling agent modified mineral fillers
Mixing a silane coupling agent KH-550 and 60 wt% of ethanol according to a volume ratio of 1:60 to obtain a silane coupling agent solution; and (2) soaking the calcium carbonate whiskers in a silane coupling agent solution for 60min, taking out the calcium carbonate whiskers and the silane coupling agent solution according to the mass ratio of 1:5, and drying the calcium carbonate whiskers in a drying oven at 100 ℃ to prepare the silane coupling agent modified calcium carbonate whiskers.
Mixing a silane coupling agent KH-550 and 70 wt% of ethanol according to the volume ratio of 1:50 to obtain a silane coupling agent solution; and soaking the silicon carbide crystal whiskers in a silane coupling agent solution for 60min, taking out the silicon carbide crystal whiskers and the silane coupling agent solution in a mass ratio of 1:6, and drying the silicon carbide crystal whiskers in a drying oven at 100 ℃ to prepare the silane coupling agent modified silicon carbide crystal whiskers.
Microcapsule type flame retardant 1
S1: taking 50g of bisphenol A epoxy resin E44 (epoxy equivalent 190), adding 200mL of absolute ethyl alcohol, and stirring until the absolute ethyl alcohol is dissolved for later use;
s2: dispersing 200g of flame retardant triphenyl phosphate and triisobutyl phosphate in total in absolute ethyl alcohol under the stirring state at room temperature to obtain a mixed solution, and adding a bisphenol A epoxy resin solution when the temperature is raised to 40 ℃;
s3: weighing 24g of polyether amine curing agent (active hydrogen equivalent 80) and dissolving in a proper amount of water to obtain a curing agent solution, dropwise adding the curing agent solution into the mixed solution obtained in the step S2, slowly heating to 65 ℃, keeping the reaction for 6 hours, cooling to room temperature, washing and centrifuging until the upper layer liquid is colorless and transparent, drying and dispersing the precipitate, and thus obtaining the microcapsule type flame retardant.
Microcapsule type flame retardant 2
The preparation raw materials and the preparation method are the same as the microcapsule flame retardant 1, and the difference is only in the step S1, namely 45g of bisphenol A epoxy resin E44 (epoxy equivalent 190) and 5g of cage type octa (2, 3-glycidoxypropyl) POSS are taken, 200mL of absolute ethyl alcohol is added, and the mixture is stirred until the absolute ethyl alcohol is dissolved for standby.
Microcapsule type flame retardant 3
The preparation raw materials and the preparation method are the same as the microcapsule flame retardant 1, and the difference is only in the step S1, namely 40g of bisphenol A epoxy resin E44 (epoxy equivalent 190) and 10g of cage type octa (2, 3-glycidoxypropyl) POSS are taken, 200mL of absolute ethyl alcohol is added, and the mixture is stirred until the absolute ethyl alcohol is dissolved for standby.
Microcapsule type flame retardant 4
The preparation raw materials and the preparation method are the same as those of the microcapsule flame retardant 1, and the difference is only in the step S1, namely 36g of bisphenol A epoxy resin E44 (epoxy equivalent 190) and 14g of cage type octa (2, 3-glycidoxypropyl) POSS are taken, 200mL of absolute ethyl alcohol is added, and the mixture is stirred until the absolute ethyl alcohol is dissolved for standby.
Preparation example of high CTI halogen-free flame retardant polycarbonate material
Example 1
The high CTI halogen-free flame-retardant polycarbonate material comprises the following components:
Figure BDA0003409343020000111
the preparation method of the high CTI halogen-free flame-retardant polycarbonate material comprises the following steps:
s1: drying polycarbonate (with a melt index of 15g/10min) at 110 ℃ for 3 hours, and stirring the dried polycarbonate, silane coupling agent modified glass fiber, microcapsule type flame retardant 1, styrene grafted maleic anhydride, methyl methacrylate-butadiene-styrene copolymer, antioxidant 1010, antioxidant 1076, antioxidant 168, pentaerythritol stearate and silicone powder in a high-speed stirrer for 5 minutes at the rotation speed of 1000-1200 rpm;
s2: adding the mixed material obtained in the step S1 into a double-screw extruder, and performing melt extrusion granulation, wherein the temperature of each section of the extruder is as follows: the first region is 200-210 ℃, the second region is 210-220 ℃, the third region is 220-230 ℃, and the fourth region is 230-240 ℃ to obtain the high CTI halogen-free flame-retardant polycarbonate material.
Example 2
The preparation method of the high CTI halogen-free flame-retardant polycarbonate material is the same as that of the embodiment 1, and the components are as follows:
Figure BDA0003409343020000121
example 3
The preparation method of the high CTI halogen-free flame-retardant polycarbonate material is the same as that of the embodiment 1, and the components are as follows:
Figure BDA0003409343020000122
Figure BDA0003409343020000131
example 4
The raw materials and the method for preparing the high CTI halogen-free flame-retardant polycarbonate material are the same as those in example 3, and the difference is only that the microcapsule type flame retardant 2 is replaced by the microcapsule type flame retardant 3 with the same mass.
Example 5
The raw materials and the method for preparing the high CTI halogen-free flame-retardant polycarbonate material are the same as those in the example 3, and the difference is only that the microcapsule type flame retardant 2 is replaced by the microcapsule type flame retardant 4 with the same mass.
Comparative example 1
The raw materials and the method for preparing the high CTI halogen-free flame-retardant polycarbonate material are the same as those in example 3, except that 0.5kg of unmodified glass fiber and 1.5kg of unmodified silicon carbide whisker are added.
Comparative example 2
The raw materials and the method for preparing the high CTI halogen-free flame-retardant polycarbonate material are the same as those in example 3, except that the microcapsule type flame retardant 2 is replaced by 0.48kg of phosphorus flame retardant with the same mass and without any treatment, namely 0.28kg of triphenyl phosphate and 0.2kg of triisobutyl phosphate.
Examples of effects
(1) Flame retardancy test
The halogen-free flame-retardant polycarbonate material with high CTI prepared in the embodiments 1-5 and the comparative embodiments 1-3 of the invention is prepared into sample strips with the diameter of 125mm multiplied by 13mm, the sample strips are pretreated according to the UL94 standard, the detection is carried out according to the test program, 5 samples are detected in each group, the optimal value is selected, and the result is shown in the following table:
TABLE 1 flame retardancy results for polycarbonate materials
Flame retardant rating Time to flame-out Ignition temperature of sample
Example 1 V0 30s 800℃
Example 2 V0 27s 812℃
Example 3 V0 25s 815℃
Example 4 V0 22s 824℃
Example 5 V0 20s 835℃
Comparative example 1 V0 27s 810℃
Comparative example 2 V1 41s 750℃
From the above fire resistance data, it can be seen that the fire resistance grades of the polycarbonate materials prepared by the method are all V0 grades, which meet the requirements of preparing electronic and electric appliances, and only the fire resistance grade of the comparative example 2 is V1, because the comparative example 2 is the polycarbonate prepared by directly doping the fire retardant without any treatment, the flame resistance of the microcapsule type fire retardant provided by the invention is remarkably improved compared with the conventional fire retardant. Next, as can be seen from the comparison of the data in examples 1 to 5, the flame retardant effect of example 5 is the best, which shows that the effect of using the combination of bisphenol a epoxy resin and epoxy based POSS as the capsule wall is better than the effect of using only bisphenol a epoxy resin as the capsule wall in the preparation of microcapsule type flame retardant, and the flame retardant effect is also improved to a small extent when the specific gravity of epoxy based POSS is increased. Because the epoxy group POSS can assist the bisphenol A epoxy resin to play a better protection role on the flame retardant, the epoxy group POSS also has certain flame retardant property.
(2) Tracking Index (CTI) detection
The halogen-free flame-retardant polycarbonate material with high CTI prepared in the embodiments 1-5 and the comparative embodiments 1-3 of the invention is taken as an experimental object, the CTI of the material is detected, and the results are shown in the following table.
TABLE 2 CTI results for polycarbonate materials
CTI
Example 1 420V
Example 2 426V
Example 3 425V
Example 4 425V
Example 5 427V
Comparative example 1 425V
Comparative example 2 426V
As can be seen from the data in the table above, the polycarbonate material prepared by the method provided by the invention has CTI values of more than 420V, which are higher than the requirements of unattended electronic devices proposed by IEC organization, and is suitable for manufacturing equipment in the field of electronic and electrical appliances.
(3) Mechanical property detection
The results of testing the tensile strength and the bending strength of the materials according to the standards ASTM D638 and ASTM D790 using the high CTI halogen-free flame retardant polycarbonate materials prepared in examples 1-5 of the present invention and comparative examples 1-3 as experimental objects are shown in the following table.
TABLE 3 mechanical Property results for polycarbonate materials
Tensile strength Bending strength
Example 1 104MPa 156MPa
Example 2 106MPa 161MPa
Example 3 113MPa 170MPa
Example 4 120MPa 177MPa
Example 5 127MPa 183MPa
Comparative example 1 95MPa 140MPa
Comparative example 2 81MPa 124MPa
From the above table of mechanical properties of polycarbonate materials, it can be seen that the polycarbonate prepared by the method of the present invention has significantly improved tensile strength and bending strength compared to the polycarbonate directly doped with glass fiber or mineral filler (comparative example 1) whose surface is not modified. Secondly, the method of directly adding the flame retardant into the material (comparative example 2) has great influence on the mechanical property of the material, and the invention advocates that the mechanical property is obviously improved by preparing the flame retardant into a microcapsule form. In addition, the mechanical data of examples 1-5 can demonstrate that the improvement of mechanical properties by using bisphenol-a epoxy resin and epoxy-based POSS as microcapsule walls during the preparation of microcapsule-type flame retardants is better than that of bisphenol-a epoxy resin alone. And when the content of the epoxy POSS is increased, the mechanical property of the prepared polycarbonate also shows an increasing trend, and the polycarbonate has better stress cracking resistance.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (4)

1. The high CTI halogen-free flame retardant polycarbonate material is characterized by comprising the following components in parts by weight: 70-80 parts of polycarbonate, 15-20 parts of modified reinforcing agent, 5-6 parts of flame retardant, 5-8 parts of toughening agent, 0.1-0.3 part of antioxidant and 0.1-0.5 part of lubricant; the polycarbonate is bisphenol A polycarbonate, the melt index is 15-30g/10min, the modification reinforcing agent is silane coupling agent modified glass fiber and/or silane coupling agent modified mineral filler, the diameter of the glass fiber is 10-15 mu m, and the mineral filler comprises at least one of calcium carbonate whisker, calcium sulfate whisker and silicon carbide whisker;
the silane coupling agent modified glass fiber and the silane coupling agent modified mineral filler are prepared by the following method: soaking the glass fiber and/or mineral filler in a silane coupling agent solution for 30-60min, taking out and drying, and uniformly dispersing; the mass ratio of the glass fiber and/or mineral filler to the silane coupling agent solution is 1: (5-7);
the toughening agent is selected from the combination of styrene grafted maleic anhydride and methyl methacrylate-butadiene-styrene copolymer, and the mass ratio is (1-3): 1; the antioxidant is selected from the compound of an antioxidant 1010, an antioxidant 1076 and an antioxidant 168, and the mass ratio of the antioxidant 1010: antioxidant 1076: antioxidant 168 ═ 1: 1: (1-1.5); the lubricant is selected from any one or the combination of more than two of fatty acid ester lubricant, paraffin lubricant and organosiloxane lubricant;
the flame retardant is a microcapsule type flame retardant prepared by coating a capsule core with a capsule wall, the mass ratio of the capsule wall to the capsule core is (0.1-0.4):1, the capsule core is a phosphorus flame retardant, and the phosphorus flame retardant comprises one or a combination of more than two of triphenyl phosphate, triisobutyl phosphate and tricresyl phosphate; the capsule wall is a cured product obtained by reacting bisphenol A epoxy resin and a curing agent, wherein the bisphenol A epoxy resin is selected from one or a combination of two of E44, E51 and E54, the epoxy equivalent is 160-190, the curing agent is a polyether amine curing agent or a polyamide curing agent, and the active hydrogen equivalent is 50-80;
the capsule wall also comprises epoxy cage-type silsesquioxane, the epoxy POSS is a compound shown as a formula I,
Figure FDA0003809547330000021
r is 2, 3-glycidoxypropyl and 3, 4-epoxycyclohexylethyl;
the capsule wall is a cured product obtained by reacting bisphenol A epoxy resin, epoxy group POSS and a curing agent, wherein the mass ratio of the bisphenol A epoxy resin to the epoxy group POSS is 1: (0.1-0.4);
the microcapsule type flame retardant is prepared by the following method:
(1) dispersing a phosphorus flame retardant in a solvent under a stirring state to obtain a mixed solution, heating to 35-45 ℃, and adding a bisphenol A epoxy resin and an epoxy group POSS solution, wherein the solvent is one or a combination of two of methanol, absolute ethyl alcohol, butanol and chloroform;
(2) weighing a curing agent, dissolving the curing agent in water to obtain a curing agent solution, dropwise adding the curing agent solution into the mixed solution obtained in the step (1), gradually heating to 60-65 ℃, and keeping the reaction for 6-7 hours; and cooling to room temperature, washing and centrifuging until the upper layer liquid is colorless and transparent, drying and dispersing the precipitate, and preparing the microcapsule type flame retardant.
2. The high CTI halogen-free flame retardant polycarbonate material of claim 1, wherein the lubricant is a combination of pentaerythritol stearate and silicone powder, and the mass ratio is 1: (0.2-0.5).
3. A method for preparing the high CTI halogen-free flame retardant polycarbonate material of claim 1, the method comprising the steps of:
(1) drying the polycarbonate at the temperature of 100-;
(2) and (2) adding the mixed material obtained in the step (1) into a double-screw extruder, and performing melt extrusion and granulation to obtain the high CTI halogen-free flame-retardant polycarbonate material.
4. Use of the halogen-free flame retardant polycarbonate material with high CTI as claimed in claim 1 in the preparation of engineering plastics in the field of electronics.
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* Cited by examiner, † Cited by third party
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CN112341779A (en) * 2020-10-21 2021-02-09 工业和信息化部电子第五研究所华东分所 High CTI halogen-free flame-retardant reinforced polycarbonate and preparation method and application thereof

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