CN109251502A - A kind of polycarbonate based composites and its preparation method and application - Google Patents
A kind of polycarbonate based composites and its preparation method and application Download PDFInfo
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- CN109251502A CN109251502A CN201810865307.6A CN201810865307A CN109251502A CN 109251502 A CN109251502 A CN 109251502A CN 201810865307 A CN201810865307 A CN 201810865307A CN 109251502 A CN109251502 A CN 109251502A
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Abstract
The present invention discloses a kind of polycarbonate based composites and its preparation method and application, it is related to technical field of material modification, to improve fast light xanthochromia performance, low-temperature flexibility and structural strength of the plastic part made by polycarbonate in long-term UV environment and keep the good heat-resistant deforming performance of PC material.The polycarbonate based composites use is made as following formula；The formula includes at least polycarbonate, ultraviolet absorbing agent, silicon systems toughener and PMMA/ Nano-meter SiO_22Type toughening agent with core-shell structure.The preparation method of the polycarbonate based composites is used to prepare above-mentioned polycarbonate based composites.Polycarbonate based composites provided by the invention and its preparation method and application are in yellowing-resistant plastic part.
Description
Technical Field
The invention relates to the technical field of material modification, in particular to a polycarbonate-based composite material and a preparation method and application thereof.
Background
Bisphenol a Polycarbonate (abbreviated as PC) is a thermoplastic resin prepared by transesterification of bisphenol a with diphenyl carbonate or polycondensation with phosgene (chlorine carbonate). Polycarbonate has good heat resistance, flame retardance and excellent mechanical property, so that polycarbonate is frequently applied to plastic parts of electrical products such as wall switches, converters, LED down lamps and digital products.
When the color of the plastic part of the electrical product made of the polycarbonate is white, the plastic part made of the polycarbonate has the problem of obvious light yellowing after long-term use in an ultraviolet environment.
In order to solve the problem that plastic parts made of polycarbonate have obvious light yellowing after being used in an ultraviolet environment for a long time, an ultraviolet absorbent is generally added into the polycarbonate to obtain a polycarbonate-based composite material. However, the light yellowing resistance of plastic parts made of polycarbonate-based composite materials is still not very good, and the problems of reduced toughness and poor heat distortion resistance occur
Disclosure of Invention
The invention aims to provide a polycarbonate-based composite material, and a preparation method and application thereof, so as to improve the light yellowing resistance, low-temperature toughness and structural strength of a plastic part made of polycarbonate in a long-term ultraviolet environment and maintain good heat-resistant deformation performance of a PC material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polycarbonate-based composite material is prepared by adopting the following formula; the formula at least comprises polycarbonate, an ultraviolet absorbent, a silicon toughener and PMMA/nano SiO2A core-shell structure toughening agent.
Compared with the prior art, the polycarbonate-based composite material provided by the invention not only comprises polycarbonate and an ultraviolet absorber, but also comprises a silicon-based toughening agent and PMMA/nano SiO2Core-shell structure toughening agent, silicon toughening agent and PMMA/nano SiO2The synergistic effect of the core-shell structure toughening agent can not only effectively improve the low-temperature toughness of the polycarbonate-based composite material, but also utilize the silicon toughening agent and PMMA/nano SiO2The siloxane group and the acrylic group contained in the core-shell structure toughening agent improve the light yellowing resistance of the polycarbonate-based composite material. Furthermore, since PMMA/nano SiO2The core-shell structure toughening agent not only contains nano silicon dioxide with higher surface energy, but also contains polymethyl Methacrylate (PMMA), which is an acrylic material, so PMMA/nano SiO can be utilized2The nano silicon dioxide contained in the core-shell structure toughening agent enables the silicon toughening agent and PMMA/nano SiO2The core-shell structure toughening agent can be uniformly dispersed in the polycarbonate material to obtain good toughening effect, thereby reducing the content of silicon toughening agent and PMMA/nano SiO2The using amount of the core-shell structure toughening agent avoids the silicon toughening agent and PMMA/nano SiO2Toughening of core-shell structureThe heat distortion temperature of the material is sharply reduced and the anti-photoyellowing performance is obviously deteriorated due to the addition of a large amount of the agent. Furthermore, PMMA/nano SiO is utilized2PMMA contained in core-shell structure toughening agent, silicon toughening agent and PMMA/nano SiO2The silicon element contained in the composite toughening system formed by the core-shell structure can improve the surface hardness of plastic parts made of the polycarbonate-based composite material. Therefore, compared with the prior art, the plastic part made of the polycarbonate-based composite material provided by the invention maintains the good thermal deformation resistance of the polycarbonate material, and simultaneously improves the light yellowing resistance, low-temperature toughness, structural strength and surface hardness of the plastic part.
The invention also provides a preparation method of the polycarbonate-based composite material, which comprises the following steps:
the formula of the polycarbonate-based composite material at least comprises polycarbonate, an ultraviolet absorbing material, a silicon toughening agent and PMMA/nano SiO2And melting and plasticizing the core-shell structure toughening agent to obtain the polycarbonate-based composite material.
Compared with the prior art, the preparation method of the polycarbonate-based composite material provided by the invention has the same beneficial effects as the polycarbonate-based composite material in the technical scheme, and the detailed description is omitted.
The invention also provides an application of a plastic part prepared from the polycarbonate-based composite material in an electrical product.
Compared with the prior art, the beneficial effects of the application provided by the invention are the same as those of the polycarbonate-based composite material in the technical scheme, and are not repeated herein.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a flow chart of a method for preparing a polycarbonate-based composite material according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
In the prior art, polycarbonate has good heat resistance and flame retardance, and can pass a ball pressure test of an electrical product on a current-carrying component at 125 ℃, and when a plastic part prepared by polycarbonate without adding a flame retardant is subjected to a flammability test, the temperature of a glow wire is 770 ℃, and the flammability grade of the plastic part reaches UL94V 2. Based on the characteristics of good heat resistance and flame retardance of polycarbonate, polycarbonate is mostly selected as plastic parts used by electrical products. However, due to the poor weather resistance of polycarbonate, when the white plastic made of polycarbonate is applied to an electrical product, the electrical product is in an open air environment with strong ultraviolet rays for a long time and is easy to have obvious light yellowing problem. For example: plastic parts used by electrical products such as wall switch panels, converter shells used outdoors, digital product shells and the like are made of polycarbonate, and the plastic parts used by the electrical products turn yellow after being used in the outdoor strong ultraviolet environment for a long time, so that a large number of customers complain.
In order to solve the problem that plastic parts made of polycarbonate have obvious light yellowing after being used in an ultraviolet environment for a long time, an ultraviolet absorbent is generally added into the polycarbonate to obtain a polycarbonate-based composite material. However, the light yellowing resistance of plastic parts made of polycarbonate-based composite materials is still not good, and the dual reduction of low-temperature toughness and structural strength occurs, so that the plastic parts made of polycarbonate-based composite materials have the problems of obvious light yellowing, poor low-temperature toughness and poor scratch resistance of the plastic parts in a long-term ultraviolet environment. And in order to improve the low-temperature toughness of the plastic part made of the polycarbonate-based composite material, if a toughening agent is added into the polycarbonate-based composite material, the light yellowing resistance and the heat deformation temperature of the plastic part made of the polycarbonate-based composite material are reduced.
In view of the above problems, embodiments of the present invention provide a polycarbonate-based composite material, which is prepared according to the following formulation. The formula at least comprises polycarbonate, ultraviolet absorption material, silicon toughener and PMMA/nano SiO2A core-shell structure toughening agent.
Specifically, the formula at least comprises polycarbonate, ultraviolet absorption material, silicon toughener and PMMA/nano SiO by adopting a melting plasticizing method2And melting and plasticizing the core-shell structure toughening agent to obtain the polycarbonate-based composite material.
As known from the formula and the preparation method of the polycarbonate-based composite material, the formula of the polycarbonate-based composite material not only comprises polycarbonate and an ultraviolet absorber, but also comprises a silicon-based toughening agent and PMMA/nano SiO2Core-shell structure toughening agent, silicon toughening agent and PMMA/nano SiO2The synergistic effect of the core-shell structure toughening agent can not only effectively improve the low-temperature toughness of the polycarbonate-based composite material, but also utilize the silicon toughening agent and PMMA/nano SiO2The siloxane group and the acrylic group contained in the core-shell structure toughening agent improve the light yellowing resistance of the polycarbonate-based composite material. Furthermore, since PMMA/nano SiO2The core-shell structure toughening agent not only contains nano silicon dioxide with higher surface energy, but also containsAnd also contains polymethyl Methacrylate (PMMA), so PMMA/nano SiO can be used2The nano silicon dioxide contained in the core-shell structure toughening agent enables the silicon toughening agent and PMMA/nano SiO2The core-shell structure toughening agent can be uniformly dispersed in the polycarbonate material, so that the polycarbonate-based composite material obtains good toughening effect, and the silicon toughening agent and PMMA/nano SiO are reduced2The using amount of the core-shell structure toughening agent avoids the silicon toughening agent and PMMA/nano SiO2The thermal deformation temperature of the material is sharply reduced and the anti-photoyellowing performance is obviously deteriorated due to the large amount of the core-shell structure toughening agent. Furthermore, PMMA/nano SiO is utilized2PMMA and silicon series toughening agent and PMMA/nano SiO contained in core-shell structure toughening agent2The silicon element contained in the composite toughening system formed by the core-shell structure can improve the surface hardness of plastic parts made of the polycarbonate-based composite material. . Therefore, compared with the prior art, the plastic part made of the polycarbonate-based composite material provided by the embodiment of the invention maintains the good thermal deformation resistance of the polycarbonate material, and simultaneously improves the light yellowing resistance, low-temperature toughness, structural strength and surface hardness of the plastic part.
Specifically, in consideration of the problem that the addition amount of a common toughening agent is large, the light yellowing resistance and the thermal deformation resistance of a plastic part made of the prepared polycarbonate-based composite material are poor, the formula adopted by the polycarbonate-based composite material provided by the embodiment of the invention selects the silicon toughening agent and the PMMA/nano SiO2The core-shell structure toughener enables the silicon toughener to play a main toughening function and pass through PMMA/nano SiO2The nano silicon dioxide contained in the core-shell structure toughening agent has the characteristic of higher surface energy, and the silicon toughening agent is promoted to be dispersed in the polycarbonate, so that the silicon toughening agent and PMMA/nano SiO2The toughening effect of the core-shell structure toughening agent is fully exerted; at the same time, PMMA/nano SiO2Nano silicon dioxide contained in core-shell structure toughening agentHas higher surface energy and can also ensure that PMMA/nano SiO in which the material is positioned2The core-shell structure toughening agent is fully dispersed in the polycarbonate, so that PMMA/nano SiO2The structural strength of the plastic part made of the polycarbonate-based composite material is improved while the silicon-based toughening agent is assisted by the core-shell structure toughening agent to toughen. Moreover, the silicon toughener and PMMA/nano SiO2The composite toughening system formed by the core-shell structure toughening agent contains siloxane group and PMMA, so that when the silicon toughening agent and the PMMA/nano SiO are used as the toughening agent2When the composite toughening system formed by the core-shell structure toughening agent contains siloxane and PMMA which are fully dispersed in polycarbonate, the light yellowing resistance of a plastic part made of the polycarbonate-based composite material can be effectively improved. Based on the above, compared with the traditional polycarbonate-based composite material, the polycarbonate-based composite material provided by the embodiment of the invention has the advantages that the silicon-based toughening agent and the PMMA/nano SiO2The addition amount of the core-shell structure toughening agent is small, so that the light yellowing degree of plastic parts made of polycarbonate when the addition amount of the traditional rubber toughening agent is large is relieved, and the problem that the heat deformation resistance of the plastic parts made of polycarbonate is reduced when the addition amount of the traditional rubber toughening agent is large is also inhibited; meanwhile, the polycarbonate-based composite material contains a silicon-based toughening agent and PMMA/nano SiO2The addition amount of the core-shell structure toughening agent is less, so that the preparation cost of the polycarbonate-based composite material is reduced to a certain extent.
In other words, due to PMMA/nano SiO2The core-shell structure toughening agent not only has the function of auxiliary toughening, but also contains nano silicon dioxide which can lead the ultraviolet absorbent and PMMA/nano SiO2The core-shell structure toughening agent, the silicon toughening agent and the polycarbonate have good compatibility, so that the polycarbonate, the ultraviolet absorbent, the silicon toughening agent and the PMMA/nano SiO2During the melting and plasticizing process of the core-shell structure toughening agent, polycarbonate, ultraviolet absorbent, silicon toughening agent and PMMA/nano SiO2The core-shell structure toughening agents can be fully contacted, so that the obtained polycarbonate-based composite material is ensuredThe manufactured plastic part has good low-temperature toughness, structural strength and light yellowing resistance, and keeps good thermal deformation resistance; therefore, a plastic part manufactured by the formula used in the polycarbonate-based composite material provided by the embodiment of the invention has good light yellowing resistance, good low-temperature toughness and scratch resistance in a long-term ultraviolet environment, and keeps the polycarbonate material having good heat deformation resistance. Therefore, when the plastic part manufactured by the formula used by the polycarbonate-based composite material provided by the embodiment of the invention is applied to an electrical product, the anti-aging performance of the plastic part in the electrical product in an environment with stronger ultraviolet light can be improved.
In addition, when the formula is used for preparing the polycarbonate-based composite material in a double-screw extruder mode, a part of the silicon-based toughening agent contained in the formula can generate dehydration hinge reaction with a polycarbonate molecular chain under the secondary action of higher extrusion temperature and injection molding temperature, so that the end capping effect on the polycarbonate molecular chain is achieved, and the weather resistance of the polycarbonate is improved.
Furthermore, when the silicon contained in the silicon-based toughening agent exists in the form of siloxane group, the siloxane group can also improve the low-temperature toughness of the material in the process that the silicon-based toughening agent and the polycarbonate molecular chain undergo dehydration reaction.
Illustratively, the polycarbonate, the silicon-based toughening agent and the PMMA/nano SiO2The mass ratio of the core-shell structure toughening agent is (75-95): (1-7): 0.5-4). When polycarbonate, silicon toughener and PMMA/nano SiO2The mass ratio of the core-shell structure toughening agent is in the range, so that the added silicon toughening agent and the PMMA/nano SiO can be ensured2And under the condition of less core-shell structure materials, the light yellowing resistance, low-temperature toughness and material hardness of the polycarbonate-based composite material are effectively improved. In addition, to avoid PMMA/nano SiO2The problem of increased brittleness of the material caused by excessive addition of PMMA (polymethyl methacrylate) contained in the core-shell structure material is solved by the polycarbonate-based composite material provided by the embodiment of the inventionIn the formula, PMMA/nano SiO2The addition amount of the core-shell structure toughening agent is less than that of the silicon toughening agent. Furthermore, when polycarbonate, silicon toughener and PMMA/nano SiO2The mass ratio of the core-shell structure toughening agent is in the range, and the core-shell structure toughening agent can be prepared by using a silicon toughening agent and PMMA/nano SiO2The addition amount of the core-shell structure toughening agent adjusts the toughness and hardness of the plastic piece made of the polycarbonate-based composite material, so that the plastic piece made of the polycarbonate-based composite material has good structural strength and good low-temperature toughness.
The silicon-based toughening agent is one or a combination of more of a silicon-acrylic rubber toughening agent, a silicon-based toughening agent MX-520S and a silicon-based toughening agent MX-550H in any proportion. Wherein the manufacturers of the silicon series toughener MX-520S and the silicon series toughener MX-550H are Busman chemistry, and the silicon-acrylic rubber toughener is an easily-plasticized material produced by Perster New materials science and technology LimitedTMA silicon-acrylic rubber toughening agent 201.
The PMMA/nano SiO2The preparation method of the core-shell structure toughening agent is various, and in the formula used by the polycarbonate-based composite material provided by the embodiment of the invention, PMMA/nano SiO2The core-shell structure toughening agent is prepared by the following method:
under the anaerobic condition, uniformly mixing the alkylated nano-silica, polyvinylpyrrolidone and ethanol, and heating to 65-70 ℃ to obtain a mixed solution; adding a mixed solution of methyl methacrylate and an initiator into the mixed solution for reaction until the polymerization reaction of the methyl methacrylate is finished to obtain PMMA/nano SiO2A core-shell structure toughening agent; the mass ratio of the alkylated nano-silica to the methyl methacrylate contained in the mixed solution is 100 (180-250), the mass ratio of the alkylated nano-silica to the polyvinylpyrrolidone contained in the mixed solution is 100 (30-50), and the mass ratio of the methyl methacrylate to the initiator contained in the mixed solution of the methyl methacrylate and the initiator is (180-250): 6; the initiator is one or more of azobisisobutyronitrile, lauroyl peroxide and azobisisoheptonitrile.
The time required for the reaction by adding the mixed solution of methyl methacrylate and the initiator to the mixed solution until the polymerization reaction of methyl methacrylate is completed may be determined by thin layer chromatography or liquid phase monitoring, and is not further limited herein.
Illustratively, 100g of alkylated nanosilica was added to 3000mL of an aqueous ethanol solution having a mass concentration of 95%, and then 45g of polyvinylpyrrolidone was added thereto and uniformly dispersed using sonication to obtain a premix. The premix was charged into a sealed reaction vessel, and nitrogen gas was introduced into the reaction vessel. The reaction kettle was heated with an oil bath and the premix was mechanically stirred so that it was heated to 65-70 ℃. A mixed solution of methyl methacrylate and an initiator (220g of methyl methacrylate, 6g of initiator) was slowly added to the premix during stirring and reacted for 10 hours. Separating the obtained precipitate by suction filtration, centrifuging the precipitate, ultrasonically washing with anhydrous ethanol for 3 times, and vacuum drying at 55 deg.C for 24 hr to obtain PMMA/nanometer SiO2A core-shell structure toughening agent.
The preparation method of the alkylated nano silicon dioxide comprises the following steps: and (3) drying 100g of nano silicon dioxide with the particle size of 6nm-35nm for 24h in vacuum at 125 ℃ to obtain the dry nano silicon dioxide. All the dried nano-silica obtained after drying 100g of nano-silica, 3000mL of ethanol aqueous solution with the mass concentration of 95% and 55g of sulfopropyl diethanol methyl ammonium inner salt are put into a closed reaction kettle. Under the protection of nitrogen, the reaction kettle is heated by adopting an oil bath, so that a reaction system in the reaction kettle is subjected to reflux reaction for 10 hours at 90 ℃ under the mechanical stirring. After the reaction is finished, extracting the precipitate contained in the obtained reaction system, airing the precipitate, and ultrasonically cleaning the precipitate for 2 times by using absolute ethyl alcohol to remove the unreacted sulfopropyl diethanol methyl ammonium inner salt contained in the precipitate. Vacuum drying the obtained purified product at 55 ℃ for 24h to obtain the nano SiO treated by alkylation coupling2Namely the alkylated nanosilica described above.
The ultraviolet absorption band of the ultraviolet absorber can be set according to actual conditions. For example: the ultraviolet absorbing material has an ultraviolet absorbing wavelength range of 300nm to 400 nm. The ultraviolet absorption material comprises a benzotriazole weather-resistant agent, a hindered amine weather-resistant agent and a triazine weather-resistant agent, wherein the mass ratio of polycarbonate to the benzotriazole weather-resistant agent to the hindered amine weather-resistant agent to the triazine weather-resistant agent is (75-95): (0.2-2):(0.1-2):(0.1-3).
As can be seen from the above, the formula used in the polycarbonate-based composite material provided in the embodiment of the present invention not only includes the benzotriazole-based weather-resistant agent, but also includes the hindered amine-based weather-resistant agent and the triazine-based weather-resistant agent, so that the hindered amine-based weather-resistant agent and the triazine-based weather-resistant agent can adjust the ultraviolet light band absorbed by the benzotriazole-based weather-resistant agent. And the mass ratio of the benzotriazole weather resisting agent to the hindered amine weather resisting agent to the triazine weather resisting agent is (0.2-2) to (0.1-2) to (0.5-2), so that the ultraviolet absorption wavelength band of the ultraviolet absorption material is 300nm-400 nm. And the polycarbonate and the ultraviolet absorbing material comprise benzotriazole weather resisting agent, hindered amine weather resisting agent and triazine weather resisting agent in a mass ratio of (75-95): (0.5-2): (0.1-2): 0.1-3), it can be seen that, in the formula of the polycarbonate-based composite material provided by the embodiment of the invention, polycarbonate is used as a main material, and an ultraviolet absorbing material is used as an auxiliary material; when the polycarbonate-based composite material is prepared by a melting method, the benzotriazole weather-resistant agent, the hindered amine weather-resistant agent and the triazine weather-resistant agent which are contained in the ultraviolet absorbing material are dispersed in the polycarbonate, so that the prepared polycarbonate-based composite material absorbs ultraviolet rays with the wavelength of 300nm-400nm, the damage capability of the ultraviolet rays on molecules of the polycarbonate is reduced, and the light yellowing resistance of a plastic part prepared from the polycarbonate in a long-term ultraviolet environment is improved.
Meanwhile, the inventors found that: in order to increase the weather resistance of polycarbonate in the prior art, a weather-resistant auxiliary agent is added into polycarbonate, but the added weather-resistant auxiliary agent has poor effect of absorbing ultraviolet rays or has an absorption effect on ultraviolet rays in partial wave bands, and in the embodiment of the invention, three weather-resistant agents, namely a benzotriazole weather-resistant agent, a hindered amine weather-resistant agent and a triazine weather-resistant agent, are added into the polycarbonate, and the mass ratio of the polycarbonate, the benzotriazole weather-resistant agent, the hindered amine weather-resistant agent and the triazine weather-resistant agent is limited, so that the prepared polycarbonate-based composite material absorbs ultraviolet rays with the wavelength of 300nm-400nm, and the light yellowing resistance of a plastic part prepared from the polycarbonate in a long-term ultraviolet light environment is effectively improved.
The types of the above-mentioned benzotriazole-based weather resistant agents, hindered amine-based weather resistant agents and triazine-based weather resistant agents are given below by way of illustration only and are not intended to be limiting.
The benzotriazole weather-resistant agent is one or a combination of more of an ultraviolet absorbent TINUVIN 360, an ultraviolet absorbent 234, an ultraviolet absorbent THUV-328 and an ultraviolet absorbent UV-326 in any proportion. Wherein,
the ultraviolet absorbent TINUVIN 360 has the CAS number of: 103597-45-1, known as Diurethanedimethancarboxylate in English chemistry, Chinese cultural name: 2,2' -methylenebis (6- (2H-Benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol, the manufacturer may select BASF corporation, Germany, under the trade name TINUVIN 360, ultraviolet absorber 234, having CAS number 70321-86-7, full English chemical name of (2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol), Chinese name of 2- (2H-Benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, the manufacturer may select BASF corporation, under the trade name BASFTuvin 234, ultraviolet absorber THUV-328, the CAS number is: 25973-55-1, known by the English chemical name of (2- (2H-Benzotriazol-2-yl) -4, 6-ditertpentyphenol), and known by the Chinese cultural name of 2- (2H-Benzotriazol-2-yl) -4,6-ditertpentylphenol, the manufacturer may choose BASFTinuvin 328. UV-326, the CAS number of which is: 3896-11-5, chemical name in English: 2- (3-tert-Butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, the Chinese cultural name of which is 2- (2-hydroxy-3-tert-Butyl-5-methylphenyl) -5-chlorobenzotriazole, was produced by BASF TINUVIN 326.
The hindered amine weather-resistant agent is one or a combination of more of a light stabilizer Uvinul4050H, a light stabilizer TINUVIN770 and a light stabilizer 2020 in any proportion. The light stabilizer TINUVIN770 has the CAS number of: 52829-07-9, full English chemistry: bis (2,2,6, 6-tetramethyl4-piperidyl) sebacate, well-known in mesology as: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, the manufacturer may choose from basf gmbh, germany, under the trade name: BASF TINUVIN 770. Light stabilizer Uvinul4050H, CAS number: 124172-53-8, chemical name in English: n, N '- (Hexane-1,6-diyl) bis (N- (2,2,6, 6-tetramethylpiperdin-4-yl) formamide, having the name N, N' -diformyl-N, N '-bis (2,2,6, 6-tetramethyl-4-piperidine) -hexamethylenediamine, from Pasteur GmbH, Germany under the name of Pasteur photostabilizer Uvinul4050H, photostabilizer 2020 with CAS number 192268-64-7 and its name CHIMASSORB 2020, having the name 1, 6-hexanediamine, N, N' -bis (2,2,6,6-tetramethyl-4-piperidyl), 2,4, 6-trichloro-1, 3,5-triazine, N-butyl-1-butylamine, and N-butyl-2, 2,6, 6-tetramethyl-4-piperidinamine, under the trade name of Chimassorb 2020 hindered amine light stabilizer, from Pasteur GmbH, Germany.
The triazine weather resisting agent is one or a combination of more of an ultraviolet absorbent TINUVIN1600, an ultraviolet absorbent triazine-5 and octyl triazone in any proportion. Wherein, the ultraviolet absorbent TINUVIN1600 has the English chemical name: 2-hydroxypentyl-S-triazine derivative, Chinese cultural name: 2-hydroxyphenyl-S-triazine derivatives, the manufacturer being BASF GmbH, Germany. The Ultraviolet absorbent triazine-5 has the CAS number of 63856-18-8 and the chemical name of Ultraviolet absorbent triazine-5. Octyl triazone, also known as ethylhexyl triazone, has the CAS number: 88122-99-0, which is known by English chemistry as tris (2-ethylhexyl) -4,4' - (1,3,5-triazine-2,4, 6-triyltrisimino) tribeone.
In order to improve the flame retardance of polycarbonate, a large amount of flame retardant is added into polycarbonate in the prior art, but the light yellowing resistance and toughness of a plastic part made of the polycarbonate are reduced, and the plastic part is softened, so that the heat resistance and structural strength of the plastic part are reduced. In view of the above, the formulation used for the above polycarbonate-based composite material further includes: a silicon-based flame retardant. Because the flame retardant mechanism of the silicon flame retardant is a condensed phase action, when the polycarbonate-based composite material is combusted, on one hand, a combustion cracking product of the silicon flame retardant can perform a crosslinking reaction with polycarbonate, so that the crosslinked reticular polycarbonate has good heat resistance, thereby achieving the purpose of effectively inhibiting the thermal decomposition of the polycarbonate, and on the other hand, the silicon flame retardant is in a molten state, the viscosity of the generated molten substance is lower than that of the polycarbonate, so that the polycarbonate and the silicon flame retardant are separated, and the silicon flame retardant is migrated and enriched into a homogeneous flame-retardant charred layer, thereby improving the oxidation resistance of the polycarbonate, and further achieving the flame-retardant effect. Therefore, in the formula of the polycarbonate-based composite material, the polycarbonate-based composite material can meet the flame retardant requirement of the polycarbonate-based composite material only by controlling the mass ratio of the polycarbonate to the silicon-based flame retardant to be (75-95) to (0.1-2.0) and only containing a trace amount of silicon-based flame retardant, and simultaneously, the problems of light yellowing resistance reduction and softening of plastic parts made of the polycarbonate-based composite material due to the addition of a large amount of silicon-based flame retardant are avoided, so that the light yellowing resistance, the heat resistance and the structural strength of the plastic parts made of the polycarbonate-based composite material are further improved. And because the silicon flame retardant has good compatibility with the polycarbonate, the polysiloxane contained in the silicon flame retardant can be uniformly distributed in the matrix resin of the polycarbonate, so that the silicon flame retardant can better exert the effect.
In addition, the silicon flame retardant contains siloxane groups, so that the silicon flame retardant not only has the effect of improving the flame retardant property of the polycarbonate, but also has the property of resisting light yellowing.
When the polycarbonate-based composite material is prepared by using the formula in a double-screw extruder manner, a part of the silicon flame retardant contained in the formula can generate dehydration reaction with polycarbonate molecular chains under the secondary action of higher extrusion temperature and injection molding temperature, so that the end capping effect on the polycarbonate molecular chains is achieved, and the weather resistance of the polycarbonate is improved. Because the silicon flame retardant contains siloxane groups, the siloxane groups also improve the low-temperature toughness of plastic parts prepared from the polycarbonate-based composite material in the dehydration reaction process of the silicon flame retardant and polycarbonate molecular chains.
Specifically, when the formula used by the polycarbonate-based composite material contains the silicon-based toughening agent and the silicon-based flame retardant, the silicon-based toughening agent, the silicon-based flame retardant and the polycarbonate have good compatibility, so that the good dispersibility of the silicon-based flame retardant in a resin matrix of the polycarbonate can be ensured to the greatest extent, the flame retardance of the polycarbonate-based composite material is improved, and the silicon-based flame retardant, the silicon-based dyeing machine and PMMA/nano SiO are reduced to the greatest extent2The silicon element contained in the core-shell structure toughening agent has adverse effect on the toughness of the material.
In addition, in the formula used by the polycarbonate-based composite material, PMMA/nano SiO2The nano silicon dioxide contained in the core-shell structure toughening agent has higher surface energy, so that the silicon flame retardant, the silicon toughening agent and the PMMA/nano SiO2The core-shell structure toughening agent is fully dispersed in the polycarbonate to effectively play respective roles, so that the light yellowing resistance of a plastic part made of the polycarbonate-based composite material is further improved, and the low-temperature toughness and the structural strength of the plastic part are further improved.
The silicon flame retardant is FR-Si9805 organic silsesquioxane and/or polymethylsilsesquioxane. Wherein, the FR-Si9805 organic silsesquioxane flame retardant is produced by Kwangtung bunyama Kwangtze chemical engineering Co Ltd; the polymethyl silsesquioxane can be selected from BT-9273 polymethyl silsesquioxane which is produced by Guangzhou Butai chemical company, or XJY-801 polymethyl silsesquioxane which is produced by Jiangxi Xinjiayi new material company.
Optionally, the formula used for the polycarbonate-based composite material further comprises: antioxidant 1010 and antioxidant IRGANOX PS802 FD; the mass ratio of the polycarbonate to the antioxidant IRGANOX PS802 FD is (75-95): (0.1-2): 0.1-2), wherein the antioxidant 1010 is a main antioxidant, and the antioxidant IRGANOX PS802 FD is an auxiliary antioxidant. At the moment, the high-temperature injection molding performance of the material can be improved through the antioxidant 1010 and the antioxidant IRGANOX PS802 FD, and the probability of local degradation and light yellowing caused by thermal aging of plastic parts made of the polycarbonate-based composite material under the outdoor high-temperature exposure condition can be effectively reduced.
Wherein the antioxidant 1010, CAS: 6683-19-8, 2, 2-bis [ [3[3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] -1-oxopropoxy ] methyl ] -1, 3-propanediyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionate, all known as Pentaerytritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyproyl) propionate),. Irganox PS802 FL,. lTtTtTtranslation = &'s & ' gtTtTbeta& & ' & & ' TtTtTttt/Tttt & ' thiodipropionate distearate.
Optionally, the polycarbonate-based composite material further comprises an auxiliary material, wherein the auxiliary material comprises one or more of titanium dioxide, a lubricant and toner. As for the amount of the above-mentioned auxiliary materials contained in the polycarbonate-based composite material, it can be set according to the actual conditions, such as: when the auxiliary materials comprise titanium dioxide, a lubricant and a toner, the mass ratio of the polycarbonate to the titanium dioxide to the lubricant to the toner is (75-95) to (1-5) to 0.4 to (0.5-3). The lubricant can be EBS micro wax lubricant P-400 produced by Guangzhou Runfeng science and technology limited, HG-16 plastic inner lubricant produced by Hangzhou grease chemical industry limited, etc.
As shown in fig. 1, an embodiment of the present invention further provides a method for preparing a polycarbonate-based composite material, where the method for preparing the polycarbonate-based composite material includes:
at least coating the formula of the polycarbonate-based composite materialPolycarbonate, ultraviolet absorbing material, silicon toughening agent and PMMA/nano SiO2And melting and plasticizing the core-shell structure toughening agent to obtain the polycarbonate-based composite material.
Compared with the prior art, the preparation method of the polycarbonate-based composite material provided by the embodiment of the invention has the same beneficial effects as the polycarbonate-based composite material provided by the embodiment, and the details are not repeated herein.
Specifically, as shown in fig. 1, the formula of the polycarbonate-based composite material at least comprises polycarbonate, an ultraviolet absorbing material, a silicon-based toughening agent and PMMA/nano SiO2Before the core-shell structure toughening agent is melted and plasticized, the preparation method of the polycarbonate-based composite material provided by the embodiment of the invention further comprises the following steps:
step S100: the formula of the polycarbonate-based composite material at least comprises polycarbonate, an ultraviolet absorbing material, a silicon-based toughening agent and PMMA/nano SiO2Mixing the core-shell structure toughening agents to obtain a premix;
as shown in figure 1, the formula of the polycarbonate-based composite material at least comprises polycarbonate, an ultraviolet absorption material, a silicon-based toughening agent and PMMA/nano SiO2The melting and plasticizing of the core-shell structure toughening agent comprises the following steps:
step S200: and melting and plasticizing the premix by adopting a double-screw extruder, and then extruding, granulating and drying to obtain the polycarbonate-based composite material.
Wherein the screw rod of the double-screw extruder comprises a conveying section, a melting section, a mixing section, an exhaust section and a homogenizing section; the temperature of the conveying section, the melting section, the mixing section, the exhaust section and the homogenizing section is 120-270 ℃.
The embodiment of the invention also provides application of a plastic part prepared from the polycarbonate-based composite material in an electrical product, wherein the electrical product can be a switch panel and an electrical product shell. Such as a converter housing or a digital product housing for outdoor use.
Compared with the prior art, the application provided by the embodiment of the invention has the same beneficial effect as the polycarbonate-based composite material provided by the embodiment, and the detailed description is omitted here.
The heat resistance (ball pressure) of a plastic part prepared by adopting the polycarbonate-based composite material is slightly reduced, and the requirements of an electrical product on flame retardance of 870 ℃ glow wires and ball pressure of 125 ℃ of less than 1.8mm can be met.
When the plastic piece prepared from the polycarbonate-based composite material provided by the embodiment of the invention is applied to an electrical product, the electrical product meets the requirements of GB16915.1-2014 and GB 17466.1-2008. Based on the requirements of GB16915.1-2014 and GB17466.1-2008, when the plastic part made of the polycarbonate-based composite material is applied to an electrical product, the inventor sets that the plastic part in the electrical product needs to meet the following indexes:
1. IEC 60695 standard, glow wire: GWFI 870 deg.C, the time of delayed combustion after removing glow wire is less than or equal to 30s, and the silk-paper will not burn.
2. Ball pressing: 125 ℃ and the indentation is less than or equal to 1.8mm (test standard: IEC 60695)
3. The outdoor environment can not have obvious photoyellowing after being used for 3 years.
4. Tensile strength: is more than or equal to 55MPa (ISO 527, test condition 50 mm/min).
5. Bending strength: 80MPa or more (ISO 178, test condition 2 mm/min).
6. Notched izod impact strength: not less than 45KJ/m2(ISO 180, thickness 4 mm).
7. Melt index: not less than 10g/10min (ISO 1133, test conditions 300 ℃, 1.2 kg).
Several examples of the polycarbonate-based composite material are given below, and a representative polycarbonate-based composite material is selected for material property analysis.
Example one
The formula of the polycarbonate-based composite material provided by the embodiment comprises polycarbonate (Corsia PC2800), a silicon-acrylic rubber toughening agent and PMMA/nano SiO2The composite material comprises a core-shell structure toughening agent, an ultraviolet absorbent TINUVIN 360, a light stabilizer Uvinul4050H, an ultraviolet absorbent TINUVIN1600, an FR-Si9805 organic silsesquioxane flame retardant, an antioxidant 1010, an antioxidant IRGANOX PS802 FD, titanium dioxide, an EBS micro wax lubricant P-400 and toner, wherein the mass ratio of the components is 89.6:2:1.5:1:1.2:0.5:0.2:0.3:0.3:2:0.4: 1. The PMMA/nano SiO2The core-shell structure toughening agent is obtained by adopting the following method: 100g of alkylated nano-silica was added to 3000mL of an ethanol aqueous solution with a mass concentration of 95%, and then 45g of polyvinylpyrrolidone was added thereto and uniformly dispersed by ultrasonic to obtain a premix. The premix was charged into a sealed reaction vessel, and nitrogen gas was introduced into the reaction vessel. The reaction kettle was heated with an oil bath and the premix was mechanically stirred so that it was heated to 65 ℃ after the premix was heated. A mixed solution of methyl methacrylate and azobisisobutyronitrile (220g of methyl methacrylate, 6g of azobisisobutyronitrile) was slowly added to the premix while stirring for 10 hours. Separating the obtained precipitate by suction filtration, centrifuging the precipitate, ultrasonically washing with anhydrous ethanol for 3 times, and vacuum drying at 55 deg.C for 24 hr to obtain PMMA/nanometer SiO2A core-shell structure toughening agent.
The formulation adopted by the polycarbonate-based composite material provided in this example is shown in table 1 for different preparation process parameters. The performance test results of plastic parts made of the polycarbonate-based composite material provided in the first embodiment are shown in table 2 (using the first process parameter).
Example two
The formula of the polycarbonate-based composite material provided by the embodiment comprises polycarbonate (Corsia PC2800), a silicon-acrylic rubber toughening agent and PMMA/nano SiO2The composite material comprises a core-shell structure toughening agent, an ultraviolet absorbent TINUVIN 360, a light stabilizer Uvinul4050H, an ultraviolet absorbent TINUVIN1600, an FR-Si9805 organic silsesquioxane flame retardant, an antioxidant 1010, an antioxidant IRGANOX PS802 FD, titanium dioxide, an EBS micro-powder wax lubricant P-400 and toner, wherein the mass ratio of the components is 80.5:4:2.5:2:2:1:2:0.8:0.8:2:0.4: 1. The PMMA/nano SiO2The core-shell structure toughening agent is obtained by adopting the following method: 100g of alkylated nano-silica was added to 3000mL of an ethanol aqueous solution with a mass concentration of 95%, and then 45g of polyvinylpyrrolidone was added thereto and uniformly dispersed by ultrasonic to obtain a premix. The premix was charged into a sealed reaction vessel, and nitrogen gas was introduced into the reaction vessel. The reaction kettle was heated with an oil bath and the premix was mechanically stirred so that it was heated to 65 ℃ after the premix was heated. A mixed solution of methyl methacrylate and azobisisobutyronitrile (220g of methyl methacrylate, 6g of azobisisobutyronitrile) was slowly added to the premix while stirring for 10 hours. Separating the obtained precipitate by suction filtration, centrifuging the precipitate, ultrasonically washing with anhydrous ethanol for 3 times, and vacuum drying at 55 deg.C for 24 hr to obtain PMMA/nanometer SiO2A core-shell structure toughening agent.
The formulation adopted by the polycarbonate-based composite material provided in this example is shown in table 1 for different preparation process parameters. The performance test results of plastic parts made of the polycarbonate-based composite material provided in the second embodiment are shown in table 2 (using the first process parameter).
EXAMPLE III
The formula of the polycarbonate-based composite material provided by the embodiment comprises polycarbonate (Corsia PC2800), a silicon-acrylic rubber toughening agent and PMMA/nano SiO2Core-shell structure toughening agent, ultraviolet absorbent TINUVIN 360, light stabilizer Uvinul4050H, ultraviolet absorbent TINUVIN1600, FR-Si9805 organic silsesquioxane flame retardant, antioxidant 1010, antioxidant IRGANOX PS802 FD, titanium dioxide, EBS micro wax lubricant P-400 and toner, and the mass of the core-shell structure toughening agent, the ultraviolet absorbent TINUVIN 360, the light stabilizer Uvinul4050H, the ultraviolet absorbent TINUVIN1600, the FR-Si9805 organic silsesquioxane flame retardantThe ratio was 93.5:1:0.5:0.2:0.5:0.2:0.1:0.3:0.3:2:0.4: 1. The PMMA/nano SiO2The core-shell structure toughening agent is obtained by adopting the following method: 100g of alkylated nano-silica was added to 3000mL of an ethanol aqueous solution with a mass concentration of 95%, and then 45g of polyvinylpyrrolidone was added thereto and uniformly dispersed by ultrasonic to obtain a premix. The premix was charged into a sealed reaction vessel, and nitrogen gas was introduced into the reaction vessel. The reaction kettle was heated with an oil bath and the premix was mechanically stirred so that it was heated to 65 ℃ after the premix was heated. A mixed solution of methyl methacrylate and azobisisobutyronitrile (220g of methyl methacrylate, 6g of azobisisobutyronitrile) was slowly added to the premix while stirring for 10 hours. Separating the obtained precipitate by suction filtration, centrifuging the precipitate, ultrasonically washing with anhydrous ethanol for 3 times, and vacuum drying at 55 deg.C for 24 hr to obtain PMMA/nanometer SiO2A core-shell structure toughening agent.
The formulation adopted by the polycarbonate-based composite material provided in this example is shown in table 1 for different preparation process parameters. The performance test results of plastic parts made of the polycarbonate-based composite material provided in the third embodiment are shown in table 2 (using the first process parameter).
Example four
The formulation adopted by the polycarbonate-based composite material provided by the embodiment comprises polycarbonate (Corcission PC2800), silicon toughener MX-520S, PMMA/nanometer SiO2The core-shell structure toughening agent, the ultraviolet absorber 234, the light stabilizer 2020, the ultraviolet absorber triazine-5, the polymethylsilsesquioxane, the antioxidant 1010, the antioxidant IRGANOX PS802 FD, the titanium dioxide, the HG-16 plastic internal lubricant and the toner are mixed according to the mass ratio of 75:7:4:1:0.1:3:1.3:0.1:0.1:5:0.4: 3. The PMMA/nano SiO2The core-shell structure toughening agent is obtained by adopting the following method: adding 100g of alkylated nano silicon dioxide into 3000mL of ethanol water solution with the mass concentration of 95%, then adding 30g of polyvinylpyrrolidone into the ethanol water solution, and uniformly dispersing by using ultrasonic waves to obtain the nano silicon dioxideA premix. The premix was charged into a sealed reaction vessel, and nitrogen gas was introduced into the reaction vessel. The reaction kettle was heated with an oil bath and the premix was mechanically stirred so that it was heated to 70 ℃. To the premix was slowly added a mixed solution of methyl methacrylate and azobisisoheptonitrile (180g of methyl methacrylate, 6g of azobisisoheptonitrile) with stirring for 8 hours. Separating the obtained precipitate by suction filtration, centrifuging the precipitate, ultrasonically washing with anhydrous ethanol for 3 times, and vacuum drying at 55 deg.C for 24 hr to obtain PMMA/nanometer SiO2A core-shell structure toughening agent.
The temperature parameters of the formulation adopted by the polycarbonate-based composite material provided in this example in different preparation processes are shown in table 1.
EXAMPLE five
The formula of the polycarbonate-based composite material provided by the embodiment comprises polycarbonate (Corcission PC2800), a silicon toughening agent MX-550H, a silicon-acrylic rubber toughening agent and PMMA/nano SiO2The composite material comprises a core-shell structure toughening agent, an ultraviolet absorber THUV-328, a light stabilizer TINUVIN770, a light stabilizer 2020, octyl triazone, FR-Si9805 organic silsesquioxane flame retardant, polymethylsilsesquioxane, an antioxidant 1010, an antioxidant IRGANOX PS802 FD, titanium dioxide, an EBS micro-powder wax lubricant P-400 and toner in a mass ratio of 95:0.5:0.5: 0.5:1:0.5:0.05:0.15:0.1:0.1:0.1:0.5:0.5:1:0.4: 0.6. The PMMA/nano SiO2The core-shell structure toughening agent is obtained by adopting the following method: 100g of alkylated nano-silica was added to 3000mL of an ethanol aqueous solution with a mass concentration of 95%, and then 50g of polyvinylpyrrolidone was added thereto and uniformly dispersed by ultrasonic to obtain a premix. The premix was charged into a sealed reaction vessel, and nitrogen gas was introduced into the reaction vessel. The reaction kettle was heated with an oil bath and the premix was mechanically stirred so that it was heated to 67 ℃. To the premix was slowly added a mixed solution of methyl methacrylate and lauroyl peroxide (250g of methyl methacrylate) while stirring6g of lauroyl peroxide) for 8 h. Separating the obtained precipitate by suction filtration, centrifuging the precipitate, ultrasonically washing with anhydrous ethanol for 3 times, and vacuum drying at 55 deg.C for 24 hr to obtain PMMA/nanometer SiO2A core-shell structure toughening agent.
The temperature parameters of the formulation adopted by the polycarbonate-based composite material provided in this example in different preparation processes are shown in table 1.
EXAMPLE six
The formulation adopted by the polycarbonate-based composite material provided by the embodiment comprises polycarbonate (Corcission PC2800), silicon toughener MX-550H, PMMA/nanometer SiO2The paint comprises a core-shell structure toughening agent, an ultraviolet absorbent THUV-328, an ultraviolet absorbent TINUVIN 360, a light stabilizer TINUVIN770, octyl triazone, an ultraviolet absorbent triazine-5, polymethylsilsesquioxane, an antioxidant 1010, an antioxidant IRGANOX PS802 FD, titanium dioxide, an EBS micro-powder wax lubricant P-400 and toner in a mass ratio of 89.1:1:1:0.5:0.5:0.5:0.5:0.5:0.5:2:2:1:0.4: 0.5. The PMMA/nano SiO2The core-shell structure toughening agent is obtained by adopting the following method: 100g of alkylated nano-silica was added to 3000mL of an ethanol aqueous solution with a mass concentration of 95%, and then 50g of polyvinylpyrrolidone was added thereto and uniformly dispersed by ultrasonic to obtain a premix. The premix was charged into a sealed reaction vessel, and nitrogen gas was introduced into the reaction vessel. The reaction kettle was heated with an oil bath and the premix was mechanically stirred so that it was heated to 67 ℃. A mixed solution of methyl methacrylate, azobisisobutyronitrile, lauroyl peroxide (220g of methyl methacrylate, 4g of lauroyl peroxide, 2g of azobisisobutyronitrile) was slowly added to the premix while stirring for 8 hours. Separating the obtained precipitate by suction filtration, centrifuging the precipitate, ultrasonically washing with anhydrous ethanol for 3 times, and vacuum drying at 55 deg.C for 24 hr to obtain PMMA/nanometer SiO2A core-shell structure toughening agent. The polycarbonate-based composite material provided by the embodimentThe temperature parameters of the formulations used in the different preparation processes are shown in table 1.
Table 1 examples one to six provide different preparation process parameters of polycarbonate-based composites
Table 2 results of performance testing of plastic parts made of the polycarbonate-based composite materials provided in examples one, two and three
As can be seen from table 2: compared with the performance test result of the plastic part made of white polycarbonate of the existing Jettish TSM/G221AE, the light yellowing resistance, the low-temperature impact strength, the heat resistance and the structural hardness of the plastic part made of the polycarbonate-based composite material provided by the first to the third embodiments are improved to a certain extent. The plastic part made of the polycarbonate-based composite material provided by the first embodiment and the second embodiment also has good normal-temperature impact strength, but the normal-temperature impact strength of the plastic part made of the polycarbonate-based composite material provided by the third embodiment is reduced to some extent. Meanwhile, the plastic part made of the polycarbonate-based composite material provided by the first embodiment to the third embodiment has good tensile strength and bending strength, but the tensile strength and the bending strength of the plastic part made of the polycarbonate-based composite material provided by the second embodiment are reduced, so that the plastic part made of the polycarbonate-based composite material provided by the embodiment of the invention can meet the requirements of an electrical product for flame retardance of 870 ℃ glow wire and 125 ℃ ball pressure of less than 1.8 mm.
Further, silicon in polycarbonate-based compositesToughening agent, PMMA/nano SiO2Under the condition that the addition amount of the core-shell structure toughening agent and the silicon flame retardant is relatively small, the heat resistance (ball pressure) of a plastic part made of the polycarbonate-based composite material can be obviously improved. However, with the silicon toughener and PMMA/nano SiO in the polycarbonate-based composite material2The addition amounts of the core-shell structure toughening agent and the silicon flame retardant are gradually reduced, the normal-temperature and low-temperature impact strength of the plastic part made of the polycarbonate-based composite material is obviously reduced, and the surface hardness of the plastic part made of the polycarbonate-based composite material is also obviously reduced. Meanwhile, along with the silicon toughener and PMMA/nano SiO in the polycarbonate-based composite material2The content of the core-shell structure toughening agent and the silicon flame retardant is reduced, the flame retardant property of a plastic part made of the polycarbonate-based composite material is reduced remarkably (glow wire), and the critical state is reached.
In addition, as can be seen from table 2: when the polycarbonate-based composite material contains a silicon-based toughening agent and PMMA/nano SiO2The content of the core-shell structure toughening agent, the silicon flame retardant and the ultraviolet absorber is reduced at the same time, so that the light-resistant yellowing performance of a plastic part made of the polycarbonate-based composite material is greatly deteriorated. The first embodiment is the best scheme seen from actual test data, and the proportion of the toughening agent, the flame retardant and the weather-resistant agent ensures that the material has good outdoor use weather resistance and optimal cost and comprehensive properties.
As can be seen from the above, in the preparation process of the polycarbonate composite material provided in the embodiment of the present invention, the weather resistance of the polycarbonate composite material can be improved from the following three aspects, so that a plastic part made of the polycarbonate composite material is suitable for an electrical product in an outdoor long-term application scenario, and the degree of optical yellowing of the plastic part in the electrical product after being used outdoors for 3 years is equivalent to that of the plastic part made of a common material for 1 year, thereby greatly improving the optical yellowing resistance of the material.
In a first aspect: the silicon flame retardant and the silicon toughening agent are respectively subjected to dehydration reaction with the molecular chain of the polycarbonate, so that the silicon flame retardant and the silicon toughening agent are used for carrying out end capping treatment on the polycarbonate molecules, and the weather resistance of the formed polycarbonate-based composite material is improved.
In a second aspect, PMMA/nano SiO is utilized2The weather resistance of the polycarbonate-based composite material is improved by the synergistic cooperation of the core-shell structure toughening agent and the silicon toughening agent.
In the third aspect, the weather resistance of the polycarbonate-based composite material is improved by compounding three weather resistant agents, namely a benzotriazole weather resistant agent, a hindered amine weather resistant agent and a triazine weather resistant agent.
In the foregoing description of embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (16)
1. The polycarbonate-based composite material is characterized by being prepared by adopting the following formula; the formula at least comprises polycarbonate, an ultraviolet absorption material, a silicon toughening agent and PMMA/nano SiO2A core-shell structure toughening agent.
2. The polycarbonate-based composite material of claim 1, wherein the polycarbonate, the silicon-based toughener, and the PMMA/nano SiO2Mass ratio of core-shell structure toughening agent75-95 percent (1-7 percent) and 0.5-4 percent.
3. The polycarbonate-based composite material according to claim 1, wherein the silicon-based toughening agent is one or more of a silicon-acrylic rubber toughening agent, a silicon-based toughening agent MX-520S and a silicon-based toughening agent MX-550H in any proportion.
4. Polycarbonate-based composite material according to claim 1, characterized in that the PMMA/nano SiO2The core-shell structure toughening agent is prepared by the following method:
under the anaerobic condition, uniformly mixing the alkylated nano-silica, polyvinylpyrrolidone and ethanol, and heating to 65-70 ℃ to obtain a mixed solution;
adding a mixed solution of methyl methacrylate and an initiator into the mixed solution for reaction until the polymerization reaction of the methyl methacrylate is finished to obtain PMMA/nano SiO2A core-shell structure toughening agent; the mass ratio of the alkylated nano-silica to the methyl methacrylate contained in the mixed solution is 100 (180-250).
5. The polycarbonate-based composite material according to claim 4, wherein the initiator is one or more of azobisisobutyronitrile, lauroyl peroxide, azobisisoheptonitrile.
6. The polycarbonate-based composite material according to claim 1, wherein the ultraviolet absorbing material has an ultraviolet absorption wavelength band of 300nm to 400 nm.
7. The polycarbonate-based composite material according to claim 1, wherein the ultraviolet absorbing material comprises a benzotriazole-based weather-resistant agent, a hindered amine-based weather-resistant agent and a triazine-based weather-resistant agent, and the mass ratio of the polycarbonate to the benzotriazole-based weather-resistant agent to the hindered amine-based weather-resistant agent to the triazine-based weather-resistant agent is (75-95): (0.2-2):(0.1-2):(0.1-3).
8. The polycarbonate-based composite material according to claim 7, wherein the benzotriazole weather-resistant agent is one or more of an ultraviolet absorbent TINUVIN 360, an ultraviolet absorbent 234, an ultraviolet absorbent THUV-328 and an ultraviolet absorbent UV-326 which are combined in any proportion;
the hindered amine weather resistant agent is one or a combination of a plurality of light stabilizer Uvinul4050H, light stabilizer TINUVIN770 and light stabilizer 2020 in any proportion;
the triazine weather resisting agent is one or a combination of more of an ultraviolet absorbent TINUVIN1600, an ultraviolet absorbent triazine-5 and octyl triazone in any proportion.
9. The polycarbonate-based composite material according to any one of claims 1 to 8, wherein the formulation further comprises: the mass ratio of the polycarbonate to the silicon flame retardant is (75-95): 0.1-2.0).
10. Polycarbonate-based composite material according to claim 9, characterized in that the silicon-based flame retardant is FR-Si9805 organic silsesquioxane flame retardant and/or polymethylsilsesquioxane.
11. The polycarbonate-based composite material according to any one of claims 1 to 8, wherein the formulation further comprises: antioxidant 1010 and antioxidant IRGANOX PS802 FD;
the mass ratio of the polycarbonate to the antioxidant 1010 to the antioxidant IRGANOX PS802 FD is (75-95): (0.1-2): (0.1-2).
12. The polycarbonate-based composite material according to any one of claims 1 to 8, further comprising an auxiliary material, wherein the auxiliary material comprises one or more of titanium dioxide, a lubricant and a toner.
13. A method for preparing a polycarbonate-based composite material according to any one of claims 1 to 12, comprising:
the polycarbonate-based composite material as defined in any one of claims 1 to 12, which is formulated to include at least polycarbonate, an ultraviolet absorbing material, a silicon-based toughening agent and PMMA/nano SiO2And melting and plasticizing the core-shell structure toughening agent to obtain the polycarbonate-based composite material.
14. The method for preparing a polycarbonate-based composite material according to claim 13, wherein the formulation of the polycarbonate-based composite material comprises at least polycarbonate, an ultraviolet absorbing material, a silicon-based toughening agent, and PMMA/nano SiO2Before the melt plasticizing of the core-shell structure toughening agent, the preparation method of the polycarbonate-based composite material further comprises the following steps:
the formula of the polycarbonate-based composite material at least comprises polycarbonate, an ultraviolet absorbing material, a silicon-based toughening agent and PMMA/nano SiO2Mixing the core-shell structure toughening agents to obtain a premix;
the formula of the polycarbonate-based composite material at least comprises polycarbonate, an ultraviolet absorbing material, a silicon toughening agent and PMMA/nano SiO2The melting and plasticizing of the core-shell structure toughening agent comprises the following steps:
and melting and plasticizing the premix by adopting a double-screw extruder, and then extruding, granulating and drying to obtain the polycarbonate-based composite material.
15. The method for preparing a polycarbonate-based composite material according to claim 14, wherein the twin-screw extruder comprises screws including a conveying section, a melting section, a kneading section, a degassing section, and a homogenizing section; the temperature of the conveying section, the melting section, the mixing section, the exhaust section and the homogenizing section is 120-270 ℃.
16. An application of plastic parts prepared from polycarbonate-based composite material in electrical products.
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