CN113292838A - Halogen-free low-warpage low-linear-expansion-coefficient extrusion-grade thin-wall flame-retardant polycarbonate composite material and preparation method thereof - Google Patents
Halogen-free low-warpage low-linear-expansion-coefficient extrusion-grade thin-wall flame-retardant polycarbonate composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of polycarbonate resin composite materials, and discloses a halogen-free low-warpage low-linear expansion coefficient extrusion grade thin-wall flame-retardant polycarbonate material and a preparation method thereof, wherein the halogen-free low-warpage low-linear expansion coefficient extrusion grade thin-wall flame-retardant polycarbonate material comprises the following components in percentage by mass: 25.9-46.5% of PC resin, 2-4% of PET resin, 8-12% of flame retardant, 1-1.5% of toughening agent A, 1.5-3% of toughening agent B, 12-16% of mineral filler, 25-30% of glass fiber, 0.2-0.5% of anti-dripping agent, 0.1-0.3% of main antioxidant, 0.1-0.3% of auxiliary antioxidant, 0.1-0.5% of lubricant, 0.5-1% of dispersant and 3-5% of black seeds. The invention can reduce the linear expansion coefficient of the material, prevent the material from warping and deforming, solve the problems of thin-wall flame retardance and toughness balance of the material, has simple preparation method and high efficiency, can greatly save the production cost and is easy for industrial production.
Description
Technical Field
The invention relates to the technical field of polycarbonate resin composite materials, in particular to a halogen-free low-warpage low-linear-expansion-coefficient extrusion-grade thin-wall flame-retardant polycarbonate composite material and a preparation method thereof.
Background
PC resins, i.e., polycarbonate resins, have excellent mechanical properties, electrical properties, transparency, and dimensional stability, and also have good heat resistance (glass transition temperature of 150 ℃ c. and heat distortion temperature of 135 ℃ c.). Therefore, PC resins are widely used for home appliances, charger housings, or other electronic appliance accessories.
Most of the traditional television rear cover is made of ABS (acrylonitrile butadiene styrene) or PC/ABS (polycarbonate/acrylonitrile butadiene styrene), the two materials have limited heat resistance, the linear expansion coefficient is high under the condition of large heat productivity of a large-size television, the dimensional stability is poor, meanwhile, the two materials are generally processed by injection molding, an ultra-large mold is required, and the required mold is high in cost.
The television rear cover has higher requirements on the strength, toughness and flame retardance of materials, the addition of the glass fiber is an effective means for reducing the linear expansion coefficient of the PC material, but with the increase of the content of the glass fiber, the materials can have the situation of warpage deformation caused by various shrinkage anisotropy, especially extrusion-grade thin-wall large-size plates. Therefore, on one hand, reducing the linear expansion coefficient of the material and on the other hand, preventing the material from buckling deformation are one of the difficulties of the breakthrough of the material; meanwhile, due to the candlewick effect of the glass fiber, the balance of thin-wall flame retardance and toughness is another difficulty to be solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the halogen-free low-warpage low-linear-expansion-coefficient extrusion-grade thin-wall flame-retardant polycarbonate composite material and the preparation method thereof, which can reduce the linear expansion coefficient of the material, prevent the material from warping and deforming, solve the problems of thin-wall flame retardance and toughness balance of the material, have simple preparation method process and high efficiency, and can greatly save the production cost.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a halogen-free low-warpage low-linear-expansion-coefficient extrusion-grade thin-wall flame-retardant polycarbonate composite material comprises the following components in percentage by mass: 25.9-46.5% of PC (polycarbonate) resin, 2-4% of PET (polyethylene terephthalate) resin, 8-12% of flame retardant, 1-1.5% of toughening agent A, 1.5-3% of toughening agent B, 12-16% of mineral filler, 25-30% of glass fiber, 0.2-0.5% of anti-dripping agent, 0.1-0.3% of main antioxidant, 0.1-0.3% of auxiliary antioxidant, 0.1-0.5% of lubricant, 0.5-1% of dispersant and 3-5% of black seed.
The black seeds refer to black master batch taking PC (polycarbonate) as a carrier and carbon black or organic black as a filler.
When the content of the glass fiber is high, the large thin-walled product can be warped and deformed due to the shrinkage anisotropy of the glass fiber, so that the use of the product is influenced, but the low content of the glass fiber cannot play a good role in enhancing the strength of the material, so that the size of the product is unstable when the product is used in a high-temperature environment and a low-temperature environment. The polycarbonate composite material provided by the method has the advantages that the strength of the mineral filler reinforced material is properly added, and the polycarbonate composite material and the glass fiber act together, so that the linear expansion coefficient of the material is reduced, the material is prevented from warping and deforming, and the dimensional stability of the material in high and low temperature environments is ensured.
The problem of the balance between the thin-wall flame retardance and the toughness of the material is a further difficulty to be solved by the invention due to the candlewick effect of the glass fiber. When the polycarbonate composite material is extruded into a plate, the plate is required to be thinner, so that the flame retardant property of the material is ensured by adding the flame retardant, and meanwhile, the plate needs to be subjected to compression molding in the subsequent process, so that the polycarbonate composite material has certain requirements on mechanical properties, particularly the toughness of the material. However, since the flame retardant and the toughening agent are a pair of reaction bodies, the effect on the flame retardant performance of the material must be considered while improving the toughening effect.
As a further improvement of the scheme, the weight average molecular weight of the PC resin is 25000-30000 g/mol, and the melt index is 7-10 g/10 min; the intrinsic viscosity of the PET resin is 0.6-0.9 dl/g.
As a further improvement of the scheme, the fire retardant is phenoxy phosphazene fire retardant, and the phenoxy phosphazene fire retardant is one or more of hexaphenoxy triphosphazene, octaphenoxy cyclotetraphosphazene and decaphenoxy pentaphosphazene.
As a further improvement of the above scheme, the toughening agent a is an ethylene-methyl acrylate copolymer (EMA); the toughening agent B is a shell-core structure substance and consists of methyl methacrylate, acrylate and organic silicon.
By adopting the scheme, the ethylene-methyl acrylate copolymer (EMA) contains an ethylene soft chain segment, has a good toughening effect, is easy to burn and seriously affects the flame retardant effect and the linear expansion coefficient, and the shell-core structure consisting of methyl methacrylate, acrylate and organic silicon forms the toughening agent B, wherein silicon has a flame retardant synergistic effect.
As a further improvement of the above scheme, the glass fiber is flat glass fiber, the length of the glass fiber is 3-4 mm, the diameter of a long axis of a cross section which is radial to the flat glass fiber and perpendicular to the flat glass fiber is defined as a, and the diameter of a short axis of a cross section which is radial to the flat glass fiber and perpendicular to the flat glass fiber is defined as b, a: b is 4: 1, and b is more than or equal to 3 mu m.
As a further improvement of the above, the mineral filler is phlogopite, D of which50The particle size was 150 μm and the aspect ratio was 90.
By adopting the scheme, the polycarbonate composite material disclosed by the invention has the advantages that the phlogopite powder is added, the sheet layer structure of mica with the high diameter-thickness ratio plays a role in reinforcing and supporting, meanwhile, the flat glass fibers are inserted in the middle of the mica sheet layer in a penetrating manner, the two interact with each other, and the proper adding proportion and adding amount are combined, so that the comprehensive mechanical property balance of the material is realized, the material is ensured not to warp and deform, and the dimensional stability of the material is ensured.
As a further improvement of the above scheme, the primary antioxidant is at least one of hindered phenol antioxidants and aromatic amine antioxidants; the auxiliary antioxidant is at least one of phosphite antioxidant and thioester antioxidant.
By adopting the scheme, the main antioxidant can continuously play an antioxidant role for a long time by capturing free radicals generated in the plastic degradation process, the auxiliary antioxidant decomposes hydroperoxide and mainly provides heat processing stability, and a synergistic effect can be generated by using the main antioxidant and the auxiliary antioxidant together, so that the antioxidant effect is improved.
AS a further improvement of the above scheme, the anti-dripping agent is polytetrafluoroethylene coated with styrene-acrylonitrile copolymer, and the mass percentage content of the styrene-acrylonitrile copolymer is 50%, namely 50% of styrene-acrylonitrile copolymer (AS) resin is used to coat Polytetrafluoroethylene (PTFE); the lubricant is pentaerythritol stearate (PETS); the dispersing agent is silicone powder.
By adopting the scheme, the PETS has the characteristics of high specific temperature resistance, can meet the performance requirements of materials, and meanwhile, the silicone powder has good dispersibility and high temperature resistance, and can effectively disperse glass fibers and fillers to ensure that the surfaces of products do not float.
The invention provides a preparation method of the halogen-free low-warpage low-linear expansion coefficient extrusion grade thin-wall flame-retardant polycarbonate material, which comprises the following steps:
(1) drying the PC resin;
(2) mixing the dried PC resin with other components, and stirring at a high speed to obtain a uniform mixed material;
(3) and extruding and granulating the mixed material to obtain the halogen-free low-warpage low-linear expansion coefficient extrusion grade thin-wall flame-retardant polycarbonate composite material.
As a further improvement of the scheme, in the step (1), the PC resin is dried in an environment of 120-130 ℃ until the moisture content is lower than 0.02%. Because the molecular chain of the PC contains ester groups, the hydrolysis of the ester groups can be caused if moisture exists in the high-temperature processing process, so that the PC resin is dried until the moisture content is lower than 0.02 percent, the hydrolysis of the ester groups can be effectively prevented, and the quality of products is ensured.
In the step (2), high-speed stirring is completed in a high-speed stirrer; in the step (3), extrusion granulation is completed in a double-screw extruder, the processing temperature of the double-screw extruder is 240-260 ℃, and the rotating speed of a screw is 250-300 rpm/min.
Compared with the prior art, the invention has the beneficial effects that:
1. the polycarbonate composite material provided by the invention adopts the combined action of the auronite powder and the glass fiber to solve the problems of material warpage and high low-temperature expansion rate; the high aspect ratio lamellar structure of mica can play the effect that the reinforcing was supported to the material, and simultaneously, the fine interlude of flat glass is in the middle of the mica lamella, and both interact combines suitable addition proportion and addition, realizes the comprehensive mechanical properties balance of material, guarantees simultaneously that the material does not warp the deformation, guarantees its dimensional stability.
2. By adding the PET resin in a proper proportion, the polycarbonate composite material can improve the mechanical property on one hand, and can improve the melt strength when a plate is extruded on the other hand, so that an outlet die does not collapse and is normally extruded and molded;
3. the polycarbonate composite material has excellent flame retardant property and mechanical strength, and the preparation method is simple, low in production cost and easy for industrial production.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The experimental procedures, which are not specified in the following examples, are generally carried out under conventional conditions, and various common chemical reagents or samples used in the examples, unless otherwise specified, are commercially available products.
The following are descriptions of the raw materials used in the examples:
TABLE 1 sources and types of raw materials
The compositions of the polycarbonate composites of examples 1 to 5 are shown in table 2 below, and the compositions of the polycarbonate composites of comparative examples 1 to 8 are shown in table 2 below. The dosage of the components in tables 2-3 is mass percent. The weight average molecular weight of the used PC resin is 25000-30000 g/mol, the melt index is 7-10 g/10min, and the melt index test conditions are as follows: 300 ℃/1.2 kg; the intrinsic viscosity of the PET resin (polyethylene terephthalate) is 0.6-0.9 dl/g; the toughening agent A is EMA; the toughening agent B is a shell-core structure product consisting of methyl methacrylate, acrylic ester and organic silicon; the fire retardant is one or more of phenoxyphosphazenes such as hexaphenoxytriphosphazene, octaphenoxycyclotetraphosphazene or decaphenoxypentaphosphazene; the lubricant is one or more of pentaerythritol stearate (PETS) and montmorillonite wax, and is preferably pentaerythritol stearate (PETS); the mineral filler is phlogopite powder (D)50The grain diameter is 150 μm, and the ratio of the grain diameter to the thickness is 90); flat glass fiber is chopped fiber, and length is 3mm, and the definition is followed flat glass fiber is radial and is a with the major axis diameter of flat glass fiber vertically cross section, follows flat glass fiber is radial and is b, an with the minor axis diameter of flat glass fiber vertically cross section: b is 4: 1, and b is more than or equal to 3 mu m; the 50% AS coated PTFE is polytetrafluoroethylene coated by 50% of styrene-acrylonitrile copolymer by mass percentage; the antioxidant 1076 is a main antioxidant; the antioxidant 412S is an auxiliary antioxidant; the dispersing agent is silicone powder; the black seed is black master batch which takes PC (polycarbonate) as a carrier and carbon black or organic black as a filler.
TABLE 2 composition of polycarbonate composites of examples 1 to 5
TABLE 3 composition of polycarbonate composites of comparative examples 1 to 8
The preparation method of the polycarbonate composite material of the embodiment 1-5 is as follows: drying the PC resin at 120 ℃ for 4h until the water content of the PC resin is lower than 0.02%, weighing the raw materials according to the mass percentage of the components in the formula, adding the raw materials into a high-speed stirrer, adjusting the rotating speed of the stirrer to 500r/min, stirring for 5min, transferring the materials in the high-speed stirrer into a double-screw extruder, adjusting the processing temperature of the double-screw extruder to 240 ℃, adjusting the rotating speed of a screw to 300rpm/min, extruding and granulating to obtain the polycarbonate composite material of the embodiments 1-5; alternatively, the first and second electrodes may be,
drying the PC resin at 130 ℃ for 4h until the water content of the PC resin is lower than 0.02%, weighing the raw materials according to the mass percentage of the components in the formula, adding the raw materials into a high-speed stirrer, adjusting the rotating speed of the stirrer to 500r/min, stirring for 5min, transferring the materials in the high-speed stirrer into a double-screw extruder, adjusting the processing temperature of the double-screw extruder to 260 ℃ and the rotating speed of a screw to 250rpm/min, extruding and granulating to obtain the polycarbonate composite material of the embodiments 1-5.
The polycarbonate composite materials of comparative examples 1 to 8 were prepared according to the same preparation methods as in examples 1 to 5, except that the raw materials were added in the comparative examples 1 to 8 in the mass percentages of the components in table 2.
Effect embodiment:
the detection and evaluation methods of the polycarbonate composites of examples 1 to 5 and comparative examples 1 to 8 were as follows:
the polycarbonate composite materials of examples 1-5 and comparative examples 1-8 were tested for performance, and the testing procedure was: drying and injection molding the polycarbonate composite material (the process conditions of injection molding are that the temperature of a nozzle is 270 ℃, the temperatures of a metering section, a compression section and a feeding section are 265 ℃, 260 ℃ and 250 ℃, the pressure holding time is 2-4 s, and the injection pressure is 40-60 MPa), preparing a standard test sample strip, performing performance test, testing the tensile strength according to the ASTM D638 standard, the bending strength according to the ASTM D790 standard, the notch impact strength according to the ASTM D256 standard, the flame retardant property according to the UL94 standard, and the linear expansion coefficient according to the GB/T1036-shell 2008 standard, wherein the test results are shown in the following tables 4 and 5:
TABLE 4-results of Performance test of the polycarbonate composites of examples 1 to 5
TABLE 5 Performance test results for polycarbonate composites of comparative examples 1 to 8
As can be seen from the performance test results in tables 4 and 5:
by comparing the performance test results of examples 1-5 with comparative example 1, it can be known that the material cannot be molded due to the collapse of the outlet die when the sheet is extruded without adding the PET resin.
By comparing the performance test results of the examples 1-5 and the comparative example 2, it can be known that the impact strength is only 58J/M, the material is brittle, and the material is prone to crack under stress in the subsequent processing process under the condition of only adding the toughening agent B.
By comparing the performance test results of the examples 1-5 and the comparative example 3, it can be known that the flame retardant performance of the material is not qualified in the test results of UL94/0.75mm and UL94/1.0mm, and the high and low temperature cyclic warping degree is large under the condition of only adding the toughening agent A.
By comparing the performance test results of examples 1-5 and comparative examples 4-6, it can be seen that when the content of the toughening agent exceeds the content range of the present invention (e.g., comparative example 4), the flame retardant performance test result of the material is not good, the linear expansion coefficient and the high and low temperature cycle warpage are both high, when the content of the glass fiber exceeds the content range of the present invention (e.g., comparative example 5), the material is warped during extrusion and has slightly floating fiber in appearance, and when the content of the mineral filler mica exceeds the content range of the present invention (e.g., comparative example 6), the impact strength of the material is low.
By comparing the performance test results of examples 1-5 with comparative examples 7 and 8, it can be known that the mechanical properties of the material are low in tensile strength and bending strength, the high and low temperature linear expansion coefficients are large, the high and low temperature cyclic warpage is large, the mica stiffening effect is obvious, and the influence of mica on the impact strength is large under the condition that the mineral filler mica is not added or a certain amount of talcum powder is added.
The polycarbonate composite material has excellent flame retardant property and mechanical strength, the preparation method is simple, the production cost is low, the industrial production is easy, and the problems of material warpage and high and low temperature expansion rate are solved through the combined action of the mica powder and the glass fiber; the high-diameter-thickness ratio lamellar structure of the mica can play a role in reinforcing and supporting the material, meanwhile, the flat glass fibers are inserted in the middle of the mica lamellar layer, and the flat glass fibers and the mica lamellar layer interact with each other and are combined with a proper adding proportion and adding amount, so that the balance of the comprehensive mechanical properties of the material is realized, meanwhile, the material is ensured not to warp and deform, and the dimensional stability of the material is ensured; by adding the PET resin with a proper proportion, on one hand, the mechanical property can be improved, and on the other hand, the melt strength in the process of extruding the plate can be improved, so that the outlet die does not collapse and is normally extruded and molded.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and substitutions can be made without departing from the technical principle of the present invention, and these modifications and substitutions should also be regarded as the protection scope of the present invention.
Claims (10)
1. The halogen-free low-warpage low-linear-expansion-coefficient extrusion-grade thin-wall flame-retardant polycarbonate composite material is characterized by comprising the following components in percentage by mass: 25.9-46.5% of PC resin, 2-4% of PET resin, 8-12% of flame retardant, 1-1.5% of toughening agent A, 1.5-3% of toughening agent B, 12-16% of mineral filler, 25-30% of glass fiber, 0.2-0.5% of anti-dripping agent, 0.1-0.3% of main antioxidant, 0.1-0.3% of auxiliary antioxidant, 0.1-0.5% of lubricant, 0.5-1% of dispersant and 3-5% of black seeds.
2. The halogen-free low-warpage low-linear-expansion-coefficient extrusion-grade thin-wall flame-retardant polycarbonate composite material as claimed in claim 1, wherein the weight average molecular weight of the PC resin is 25000-30000 g/mol, and the melt index is 7-10 g/10 min; the intrinsic viscosity of the PET resin is 0.6-0.9 dl/g.
3. The halogen-free low-warpage low-linear-expansion-coefficient extrusion-grade thin-wall flame-retardant polycarbonate composite material as claimed in claim 1, wherein the flame retardant is a phenoxy phosphazene flame retardant, and the phenoxy phosphazene flame retardant is one or more of hexaphenoxy triphosphazene, octaphenoxy cyclotetraphosphazene and decaphenoxy pentaphosphazene.
4. The halogen-free low-warpage low-linear-expansion-coefficient extrusion-grade thin-wall flame-retardant polycarbonate composite material as claimed in claim 1, wherein the toughening agent A is an ethylene-methyl acrylate copolymer; the toughening agent B is a shell-core structure substance and consists of methyl methacrylate, acrylate and organic silicon.
5. The halogen-free low-warpage low-linear-expansion-coefficient extrusion-grade thin-wall flame-retardant polycarbonate composite material as claimed in claim 1, wherein the glass fiber is flat glass fiber, the length of the glass fiber is 3-4 mm, the diameter of a long axis of a cross section which is along the radial direction of the flat glass fiber and perpendicular to the flat glass fiber is defined as a, the diameter of a short axis of a cross section which is along the radial direction of the flat glass fiber and perpendicular to the flat glass fiber is defined as b, a: b is 4: 1, and b is more than or equal to 3 mu m.
6. The halogen-free low-warpage low-linear expansion coefficient extrusion grade thin-wall flame retardant polycarbonate composite material as claimed in claim 1, wherein the mineral filler is phlogopite, and the D of the phlogopite is50The particle size was 150 μm and the aspect ratio was 90.
7. The halogen-free low-warpage low-linear expansion coefficient extrusion grade thin-wall flame-retardant polycarbonate composite material as claimed in claim 1, wherein the main antioxidant is at least one of hindered phenol antioxidant and aromatic amine antioxidant; the auxiliary antioxidant is at least one of phosphite antioxidant and thioester antioxidant.
8. The halogen-free low-warpage low-linear-expansion-coefficient extrusion-grade thin-wall flame-retardant polycarbonate composite material as claimed in claim 1, wherein the anti-dripping agent is polytetrafluoroethylene coated with styrene-acrylonitrile copolymer, and the mass percentage of the styrene-acrylonitrile copolymer is 50%; the lubricant is pentaerythritol stearate; the dispersing agent is silicone powder.
9. The preparation method of the halogen-free low-warpage low-linear expansion coefficient extrusion grade thin-wall flame-retardant polycarbonate composite material according to any one of claims 1 to 8, characterized by comprising the following steps:
(1) drying the PC resin;
(2) mixing the dried PC resin with other components, and stirring at a high speed to obtain a uniform mixed material;
(3) and extruding and granulating the mixed material to obtain the halogen-free low-warpage low-linear expansion coefficient extrusion grade thin-wall flame-retardant polycarbonate composite material.
10. The preparation method of the halogen-free low-warpage low-linear expansion coefficient extrusion grade thin-wall flame-retardant polycarbonate composite material as claimed in claim 9, wherein in the step (1), the PC resin is dried to a moisture content of less than 0.02% in an environment of 120-130 ℃; in the step (2), high-speed stirring is completed in a high-speed stirrer; in the step (3), extrusion granulation is completed in a double-screw extruder, the processing temperature of the double-screw extruder is 240-260 ℃, and the rotating speed of a screw is 250-300 rpm/min.
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