CN113637306A - Low-temperature-resistant flame-retardant antistatic PC/PBT alloy and preparation method thereof - Google Patents
Low-temperature-resistant flame-retardant antistatic PC/PBT alloy and preparation method thereof Download PDFInfo
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Abstract
The application discloses a low-temperature-resistant flame-retardant antistatic PC/PBT alloy and a preparation method thereof, wherein the low-temperature-resistant flame-retardant antistatic PC/PBT alloy comprises the following components in percentage by mass: 30% to 78% of PC; 5 to 30 percent of PBT; 5 to 30 percent of conductive master batch; 5 to 20 percent of compound flame retardant; 5 to 20 percent of low temperature resistant toughening agent; 0.5 to 2 percent of dispersant; transesterification inhibitors 0.3% to 3%; 0.5 to 3 percent of solubilizer(ii) a 0.4 to 1 percent of antioxidant; the conductive master batch comprises 60 to 70 percent of carrier, 20 to 30 percent of carbon nano tube and 5 to 10 percent of pentaerythritol stearate according to mass percentage. The PC/PBT alloy material provided by the invention not only has the advantages of PC and PBT, but also has good flame retardance, so that a 3.2 mm-thick sample strip can vertically burn to reach UL94V-0 level, and the antistatic effect reaches the surface resistivity of 106To 1010Omega.m, the low temperature resistant effect has higher notch impact strength at the low temperature of minus 40 ℃.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, relates to a PC/PBT alloy and a preparation method thereof, and particularly relates to a low-temperature-resistant flame-retardant antistatic polycarbonate/polybutylene terephthalate (PC/PBT) alloy and a preparation method thereof.
Background
The alloy material prepared by blending and modifying the PC and the PBT has the characteristics of good electrical insulation performance, good dimensional stability, good heat resistance, good chemical corrosion resistance and the like, and is widely applied to the fields of household appliances, automobiles, electric appliance elements and the like.
Antistatic PC/PBT is taken as an important component of PC/PBT alloy, and the main method in the market at present is to add an antistatic agent into the material. The common antistatic agent is generally a non-permanent antistatic, and the addition of the antistatic agent has certain influence on the mechanical property of the material. The permanent antistatic agent has the defects of large addition amount, low impact strength, poor antistatic effect and the like, so that the application field of the material is narrow. The application of the conductive PC/PBT in the practical production is severely limited.
As an alloy material with wider application, the blended PC/PBT alloy is applied to most fields such as: the flame retardant property of the flame-retardant polypropylene composite material has higher requirements in the fields of automobiles, electronic appliances, medical equipment, sports goods and the like. Therefore, the development of the high-performance flame-retardant PC/PBT alloy material has very important significance.
Disclosure of Invention
The invention aims to provide a low-temperature-resistant antistatic flame-retardant PC/PBT alloy with good compatibility, high low-temperature impact resistance, excellent antistatic effect and higher flame-retardant performance and a preparation method thereof.
In order to solve the problems, the invention adopts the technical scheme that:
the invention provides a low-temperature-resistant flame-retardant antistatic PC/PBT alloy which is prepared from the following raw materials in percentage by mass:
the conductive master batch comprises 60 to 70 percent of carrier, 20 to 30 percent of carbon nano tube and 5 to 10 percent of pentaerythritol stearate according to mass percentage.
Optionally, the conductive master batch further includes superconducting carbon black, wherein the mass percentages of the superconducting carbon black, the carbon nanotube, the pentaerythritol stearate and the superconducting carbon black are respectively 60% to 65%, 5%, 20% to 25%, and 5% to 10%.
Optionally, the carrier is a thermoplastic resin.
Optionally, the mass percentages of the carrier, the carbon nanotube, the superconducting carbon black and the pentaerythritol stearate in the conductive master batch are 65%, 5%, 25% and 5%, and the carrier is specifically polycarbonate.
Optionally, the compound flame retardant is prepared by compounding at least two of decabromodiphenyl ether, decabromodiphenyl ethane, triphenyl phosphate (TPP), bisphenol A-Bis Diphenyl Phosphate (BDP) or Aluminum Diethylphosphinate (ADP) according to mass equal proportion.
Optionally, the compound flame retardant is triphenyl phosphate and bisphenol a-bis diphenyl phosphate, and the mass percentage range of the triphenyl phosphate and the bisphenol a-bis diphenyl phosphate is 100-300%.
Optionally, the low temperature resistant toughening agent is a methyl methacrylate-butadiene-styrene terpolymer (MBS).
Optionally, the dispersant is selected from at least one of stearic acid, OP wax or Ethylene Bis Stearamide (EBS);
the ester exchange inhibitor is selected from at least one of sodium dihydrogen phosphate, disodium dihydrogen pyrophosphate, triphenyl phosphite or sodium acid pyrophosphate (SAPP), preferably sodium dihydrogen phosphate, and is used for inhibiting the ester exchange reaction between PC and PBT.
Optionally, the solubilizer is ethylene-methyl acrylate-glycidyl methacrylate terpolymer (E-MA-GMA).
Optionally, the antioxidant is a compound of hindered phenol antioxidant 1010 and phosphite antioxidant 168 in equal proportion.
The invention also provides a preparation method of the low-temperature-resistant flame-retardant antistatic PC/PBT alloy, which comprises the following steps:
drying PC at 120-130 deg.C for 3-4 hr to control its water content below 0.02;
drying PBT at 120-140 deg.C for 3-4 hr to control its water content below 0.03;
weighing at least two of decabromodiphenyl ether, decabromodiphenyl ethane, triphenyl phosphate, bisphenol A-bis (diphenyl phosphate) or diethyl aluminum hypophosphite according to the equal weight proportion, mixing, stirring for 1 to 3 minutes, uniformly mixing, and drying the mixture for 30 to 50 minutes at 50 to 80 ℃;
weighing and uniformly mixing the dried PC 30-78%, PBT 5-30%, the compound flame retardant 5-20% and the ester exchange inhibitor 0.3-3% in percentage by weight; then adding 5 to 30 weight percent of conductive master batch, 5 to 20 weight percent of low temperature resistant toughening agent, 0.5 to 2 weight percent of dispersant, 0.5 to 3 weight percent of solubilizer and 0.4 to 1 weight percent of antioxidant, and fully mixing for 3 to 5 minutes;
and adding the mixed materials into a double-screw extruder to be fully melted and blended, wherein the melting temperature is 210-260 ℃, the rotating speed of the screw is 300-500 r/min, and extruding and granulating through the double-screw extruder to obtain the low-temperature-resistant antistatic flame-retardant PC/PBT alloy material.
Optionally, the conductive masterbatch is prepared by the following method: weighing 60 to 65 percent of carrier, 5 percent of carbon nano tube, 20 to 25 percent of superconducting carbon black and 5 to 10 percent of pentaerythritol stearate according to the mass percentage, carrying out melt blending in preparation equipment at 210 to 220 ℃, and granulating through a granulator, wherein the carbon nano tube is added for multiple times in the mixing process.
The invention has the beneficial effects that:
the low-temperature-resistant flame-retardant antistatic polycarbonate/polybutylene terephthalate (PC/PBT) alloy material disclosed by the invention has the advantages of dimensional stability, good heat resistance, good chemical corrosion resistance, high flame retardance, capability of enabling vertical combustion to reach UL94V-0 level, environmental friendliness, high low-temperature notch impact resistance, good antistatic effect and surface resistivity of 106To 1010Omega · m and good surface gloss.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of a low-temperature-resistant flame-retardant antistatic PC/PBT alloy provided by an embodiment of the application.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. This application is capable of implementation in many different ways than those herein set forth and of similar import by those skilled in the art without departing from the spirit of this application and is therefore not limited to the specific implementations disclosed below.
According to the application, the low-temperature-resistant flame-retardant antistatic PC/PBT alloy is prepared from the following raw materials in percentage by mass:
the conductive master batch comprises 60 to 70 percent of carrier, 20 to 30 percent of carbon nano tube and 5 to 10 percent of pentaerythritol stearate according to mass percentage.
In the examples of the application, the mass ratio of PC to PBT can be defined as (10-3):1, preferably (10-5): 1; the viscosity-average molecular weight of PC is 20000 to 25000. PC is used as a main resin matrix of the PC/PBT alloy, and PBT is used as a modified resin matrix, so that the defects of poor chemical resistance, difficult molding processing and the like of PC are overcome, and the defects of poor heat resistance, low impact property and large molding shrinkage rate of PBT can be overcome. The dosage proportion of the PC and the PBT is determined by combining with other raw material compositions, and if the dosage of the PC is too high and is higher than the maximum value of the range, the melt viscosity is too high in the subsequent processing process, a production device is easy to block, and the processing manufacturability is poor; if the amount of PC used is too small and less than the minimum value of the above range, there are problems that the heat resistance of the product is poor, the impact resistance is not high, and the molding shrinkage is large even if a functional assistant such as a transesterification inhibitor is added. Meanwhile, the addition of the functional additive for enhancing the non-mechanical property can also cause the reduction of the mechanical property of the product, so that the composition ratio of the resin matrix is very important to the performance of the final product.
In this embodiment, the mass ratio range of the conductive masterbatch to the total amount of PC and PBT may be further set to 1: (8-12); the conductive master batch further comprises superconducting carbon black, wherein the mass percentages of the superconducting carbon black, the carbon nanotube and the pentaerythritol stearate are respectively 60% -65%, 5% -25%, 20% -25% and 5% -10%. In an embodiment, the carrier is preferably a resin carrier, and the resin carrier is a thermoplastic resin, preferably the thermoplastic resin is polycarbonate.
In the prior art, an antistatic agent is added into a PC/PBT alloy to improve the conductivity, but the problem that the mechanical property is influenced by the large addition amount of a conductive medium exists, and in the embodiment, the conductive master batch prepared from a resin carrier, carbon nano tubes, superconducting carbon black and pentaerythritol stearate is adopted. Thermoplastic resin, particularly PC, is used as a matrix material of the master batch, so as to be beneficial to mixing and dispersing in the PC/PBT alloy; the pentaerythritol stearate is an organic matter with four same branched chains and highly symmetrical structure, and can effectively improve the fluidity, the thermal stability, the impact strength and the tensile property of a product when being used in a PC/PBT alloy; the carbon nano tubes and the carbon black are simultaneously introduced into the conductive master batches, a network structure can be formed under the isolation of the carbon black by utilizing the large length-diameter ratio of the carbon nano tubes, the conductive efficiency is improved, and the problem that the carbon nano tubes are agglomerated independently or the carbon black is independently used to cause large internal filling amount of a product is solved. Meanwhile, the PC/PBT alloy is beneficial to the tensile strength, the tear strength and the wear resistance by adding proper amounts of carbon nanotubes and carbon black. Meanwhile, the proportion and the total consumption of the carbon nano tubes and the superconducting carbon black have influence on the performances of the product such as conductivity, impact strength and the like, the consumption of the carbon nano tubes is too much and exceeds the proportion, and the problem of reduction of the conductivity and the impact strength caused by agglomeration exists, and the consumption of the carbon nano tubes is too little and is lower than the proportion, so that a conductive network is difficult to form and the use efficiency of the carbon nano tubes is reduced; if the amount of carbon black is too large, the amount of carbon black exceeds the above ratio, and the mechanical properties such as impact strength are deteriorated due to a large amount of carbon black, and if the amount of carbon black is too small, the carbon nanotubes are hardly isolated, and if the amount of carbon black is less than the above ratio, the carbon nanotubes are hardly isolated, and the conductive network is also hardly established, thereby decreasing the use efficiency of the carbon nanotubes. Preferably, the mass percentages of the carrier, the carbon nano tube, the superconducting carbon black and the pentaerythritol stearate in the conductive master batch are 65%, 5%, 25% and 5%, the carrier is specifically polycarbonate, and the carbon nano tube is a single-wall carbon nano tube.
In this embodiment, the compound flame retardant is prepared by compounding at least two selected from decabromodiphenyl ether, decabromodiphenyl ethane, triphenyl phosphate (TPP), bisphenol a-Bis Diphenyl Phosphate (BDP) or Aluminum Diethylphosphinate (ADP) in equal proportions by mass. Preferably, the compound flame retardant is triphenyl phosphate (TPP) and bisphenol A-Bis Diphenyl Phosphate (BDP), the proportion of the compound flame retardant is further optimized, and the mass percentage of the compound flame retardant and the mass percentage of the TPP and the BDP are preferably 100-300% so as to improve the flame retardant property of the low-temperature-resistant flame-retardant antistatic PC/PBT alloy.
The flame retardant rating of pure polycarbonate is generally [email protected], and the melt dripping phenomenon is serious during combustion, so that the flame retardant polycarbonate has obvious fire hazard. If no flame retardant is added into the PBT, the flame retardance of the PBT is UL94HB grade, even if phosphorus flame retardants, halogen flame retardants and the like are added to enable the flame retardance to reach UL94V-0 grade, a large amount of smoke is generated during combustion, and the phenomenon of serious melt dripping is also accompanied. At present, the flame retardant which is widely applied is a halogen flame retardant, a phosphorus flame retardant or a phosphorus-halogen composite flame retardant, or a phosphorus-nitrogen composite flame retardant. Although the halogen flame retardant has good flame retardant effect and small addition amount, the combustion product of the halogen flame retardant has certain negative effects on the environment, such as releasing toxic and corrosive hydrogen halide gas and the like; the halogen-free flame retardant such as phosphorus flame retardant has the advantages of safety, non-toxicity, low price and the like, so the application is gradually increased. However, the phosphorus-containing flame retardant system has the defects of obvious melt dripping and smoke release phenomena while having high flame retardance, which restricts the application of the phosphorus-containing flame retardant.
This example is based on a PC/PBT polymer system which gives off CO on combustion2The acid gas can be used as a gas source of the intumescent flame retardant, the PBT can be used as a carbon source of the intumescent flame retardant, the intumescent flame retardant can generate an expanded porous carbon layer on the surface of the material in the combustion process, and has the functions of oxygen isolation, heat insulation, smoke suppression and molten drop resistance, so that the intumescent flame retardant has good flame retardant property, the product performance is determined to be combined, and the specific flame retardant is added into the product to form the intumescent flame retardant in a combined manner. Therefore, a compound flame retardant consisting of TPP and BDP is selected to be added to be respectively used as an acid source and a supplementary carbon source/acid source to be combined with PC and PBT to form an intumescent flame retardant, the flame retardant effect is tested at the same time, and the mass percent of TPP and BDP is determined to be 100-300% so as to improve the flame retardant property of the low-temperature-resistant flame-retardant antistatic PC/PBT alloy.
In this embodiment, the low temperature resistant toughening agent is a methyl methacrylate-butadiene-styrene terpolymer (MBS). The processing fluidity of the PC/PBT system can be obviously improved by adding the MBS, the impact strength of the PC/PBT system is continuously increased and the tensile strength is reduced to some extent along with the increase of the use amount of the MBS, but the tensile strength is reduced to a limited extent due to the introduction of the carbon nano tubes and the carbon black in the conductive master batch, and meanwhile, the MBS has a relieving effect on the impact strength generated by the carbon nano tubes and the carbon black, namely, the MBS, the carbon nano tubes and the carbon black have complementarity in the PC/PBT system, and the improvement of the overall performance of the PC/PBT system is facilitated.
In this embodiment, the dispersant is at least one selected from stearic acid, OP wax, and Ethylene Bis Stearamide (EBS), and is preferably stearic acid. The stearic acid can effectively disperse the added functional auxiliary agent in the resin matrix, and can be used as a lubricant to reduce the melt viscosity of polycarbonate, reduce the frictional resistance between the polycarbonate and equipment and improve the processing performance of the material besides being used as a dispersing agent.
In this embodiment, the transesterification inhibitor is selected from at least one of sodium dihydrogen phosphate, disodium dihydrogen pyrophosphate, triphenyl phosphite, and sodium acid pyrophosphate (SAPP), preferably sodium dihydrogen phosphate, and the transesterification inhibitor is selected to inhibit the transesterification reaction between PC and PBT.
In this example, the solubilizer was ethylene-methyl acrylate-glycidyl methacrylate terpolymer (E-MA-GMA). In the PC/PBT system, PC is a non-crystalline copolymer, and PBT is a crystalline copolymer, so the PC/PBT system belongs to a typical non-crystalline/crystalline blending system, and poor interface adhesion and low impact strength are caused, so through tests, the addition of the solubilizer E-MA-GMA and the dosage thereof are determined.
In this embodiment, the antioxidant is a mixture of hindered phenol antioxidant 1010 and phosphite antioxidant 168 in equal proportion.
The embodiment also provides a preparation method of the low-temperature-resistant flame-retardant antistatic PC/PBT alloy, which is used for preparing the low-temperature-resistant flame-retardant antistatic PC/PBT alloy, and comprises the following steps as shown in the attached figure 1:
s101, drying the PC at the temperature of 120-130 ℃ for 3-4 hours to enable the water content of the PC to be below 0.02;
s102, drying the polybutylene terephthalate at 120-140 ℃ for 3-4 hours until the water content is below 0.03;
s103, weighing at least two of decabromodiphenyl ether, decabromodiphenyl ethane, triphenyl phosphate, bisphenol A-bis diphenyl phosphate or diethyl aluminum hypophosphite according to the equal weight proportion, mixing, stirring for 1-3 minutes to uniformly mix, and drying the mixture for 30-50 minutes at 50-80 ℃;
s104, weighing and uniformly mixing the dried PC 30-78%, PBT 5-30%, the compound flame retardant 5-20% and the ester exchange inhibitor 0.3-3% in percentage by weight; then adding 5 to 30 weight percent of conductive master batch, 5 to 20 weight percent of low temperature resistant toughening agent, 0.5 to 2 weight percent of dispersant, 0.5 to 3 weight percent of solubilizer and 0.4 to 1 weight percent of antioxidant, and fully mixing for 3 to 5 minutes;
and S105, adding the mixed materials into a double-screw extruder to be fully melted and blended, wherein the melting temperature is 210-260 ℃, the rotating speed of a screw is 300-500 r/min, and extruding and granulating through the double-screw extruder to obtain the low-temperature-resistant antistatic flame-retardant PC/PBT alloy material.
Preferably, the conductive master batch is prepared by the following steps: weighing 60-65% of carrier, 5% of carbon nano tube, 20-25% of superconducting carbon black and 5-10% of pentaerythritol stearate according to the mass percentage, carrying out melt blending in preparation equipment at 210-220 ℃, and granulating through a granulator, wherein in the mixing process, the carbon nano tube is added for multiple times. The carrier may preferably be a resin carrier, and a thermoplastic resin is more preferably used.
Example 1
A low-temperature-resistant antistatic flame-retardant PC/PBT alloy material is prepared from the following raw materials in percentage by mass: 40% of PC, 30% of PBT, 10% of conductive master batch, 12% of compound flame retardant (TPP: BDP: 3:1), 8% of low-temperature resistant toughening agent (MBS), 0.5% of dispersing agent (stearic acid), 0.3% of ester exchange inhibitor (sodium dihydrogen phosphate), 3% of solubilizer (E-MA-GMA) and 0.4% of antioxidant (antioxidant 1010 and antioxidant 168: 1). The conductive master batch is prepared by melting, mixing and granulating polycarbonate, carbon nano tubes, superconducting carbon black and pentaerythritol stearate, and the raw materials are 65%, 5%, 25% and 5% in percentage by mass in sequence.
The PC/PBT alloy is prepared by the following preparation method:
(1) drying PC at 120 deg.C for 3 hr to control water content below 0.02;
(2) drying PBT at 120 deg.C for 3 hr to control water content below 0.03;
(3) weighing TPP and BDP in proportion, putting the TPP and BDP into a high-speed mixer, stirring the mixture for 3 minutes to uniformly mix the materials, and then drying the materials for 50 minutes at the temperature of 50 ℃;
(4) weighing the dried PC, PBT, the compound flame retardant and the ester exchange inhibitor according to the weight ratio, adding the mixture into a high-speed mixer, uniformly mixing, adding the conductive master batch, the low-temperature-resistant toughening agent, the dispersing agent, the solubilizer and the antioxidant according to the mass ratio, and fully mixing for 3 minutes;
(5) and adding the mixed materials into a double-screw extruder for full melt blending, controlling the melting temperature at 260 ℃ and the rotating speed of the screw at 300 revolutions per minute, and extruding and granulating through the double-screw extruder to obtain the low-temperature-resistant antistatic flame-retardant PC/PBT alloy material.
Example 2
A low-temperature-resistant antistatic flame-retardant PC/PBT alloy material is prepared from the following raw materials in percentage by mass: 55% of PC, 15% of PBT, 10% of conductive master batch, 10% of compound flame retardant (TPP: BDP: 3:1), 10% of low-temperature resistant toughening agent (MBS), 0.5% of dispersing agent (stearic acid), 0.3% of ester exchange inhibitor (sodium dihydrogen phosphate), 3% of solubilizer (E-MA-GMA) and 0.4% of antioxidant (antioxidant 1010 and antioxidant 168: 1). The conductive master batch is prepared by melting, mixing and granulating polycarbonate, carbon nano tubes, superconducting carbon black and pentaerythritol stearate, and the mass ratio of the raw materials is 65%, 5%, 25% and 5% in sequence.
The PC/PBT alloy is prepared by the following preparation method:
(1) drying PC at 130 deg.C for 3.5 hr to control water content below 0.02;
(2) drying PBT at 120 deg.C for 3 hr to control water content below 0.03;
(3) weighing TPP and BDP in proportion, putting the TPP and BDP into a high-speed mixer, stirring the mixture for 3 minutes to uniformly mix the materials, and then drying the materials for 40 minutes at the temperature of 60 ℃;
(4) weighing the dried PC, PBT, the compound flame retardant and the ester exchange inhibitor according to the weight ratio, adding the mixture into a high-speed mixer, uniformly mixing, adding the conductive master batch, the low-temperature-resistant toughening agent, the dispersing agent, the solubilizer and the antioxidant according to the mass ratio, and fully mixing for 3 minutes;
(5) and adding the mixed materials into a double-screw extruder for full melt blending, controlling the melting temperature at 250 ℃ and the rotating speed of the screw at 350 revolutions per minute, and extruding and granulating through the double-screw extruder to obtain the low-temperature-resistant antistatic flame-retardant PC/PBT alloy material.
Example 3
A low-temperature-resistant antistatic flame-retardant PC/PBT alloy material is prepared from the following raw materials in percentage by mass: 60% of PC, 10% of PBT, 12% of conductive master batch, 8% of compound flame retardant (TPP: BDP: 3:1), 10% of low-temperature resistant toughening agent (MBS), 0.5% of dispersing agent (stearic acid), 0.3% of ester exchange inhibitor (sodium dihydrogen phosphate), 3% of solubilizer (E-MA-GMA) and 0.4% of antioxidant (antioxidant 1010 and antioxidant 168: 1). The conductive master batch is prepared by melting, mixing and granulating polycarbonate, carbon nano tubes, superconducting carbon black and pentaerythritol stearate, and the mass ratio of the raw materials is 65%, 5%, 25% and 5% in sequence.
The PC/PBT alloy is prepared by the following preparation method:
(1) drying PC at 130 deg.C for 3.5 hr to control water content below 0.02;
(2) drying PBT at 120 deg.C for 3 hr to control water content below 0.03;
(3) weighing TPP and BDP in proportion, putting the TPP and BDP into a high-speed mixer, stirring for 2 minutes to uniformly mix the materials, and then drying for 40 minutes at the temperature of 70 ℃;
(4) weighing the dried PC, PBT, the compound flame retardant and the ester exchange inhibitor according to the weight ratio, adding the mixture into a high-speed mixer, uniformly mixing, adding the conductive master batch, the low-temperature-resistant toughening agent, the dispersing agent, the solubilizer and the antioxidant according to the mass ratio, and fully mixing for 3 minutes;
(5) and adding the mixed materials into a double-screw extruder for full melt blending, controlling the melting temperature at 240 ℃ and the rotating speed of the screw at 400 rpm, and extruding and granulating through the double-screw extruder to obtain the low-temperature-resistant antistatic flame-retardant PC/PBT alloy material.
Example 4
A low-temperature-resistant antistatic flame-retardant PC/PBT alloy material is prepared from the following raw materials in parts by weight: 65% of PC, 7% of PBT, 12% of conductive master batch, 6% of compound flame retardant (TPP: BDP ═ 3:1), 10% of low temperature resistant toughening agent (MBS), 0.5% of dispersing agent (stearic acid), 0.3% of ester exchange inhibitor (sodium dihydrogen phosphate), 3% of solubilizer (E-MA-GMA) and 0.4% of antioxidant (antioxidant 1010 and antioxidant 168 ═ 1: 1). The conductive master batch is prepared by melting, mixing and granulating polycarbonate, carbon nano tubes, superconducting carbon black and pentaerythritol stearate, and the mass ratio of the raw materials is 65%, 5%, 25% and 5% in sequence.
The PC/PBT alloy is prepared by the following preparation method:
(1) drying PC at 130 deg.C for 4 hr to control water content below 0.02;
(2) drying PBT at 140 deg.C for 4 hr to control water content below 0.03;
(3) weighing TPP and BDP in proportion, putting the TPP and BDP into a high-speed mixer, stirring the mixture for 3 minutes to uniformly mix the materials, and then drying the mixture for 30 minutes at the temperature of 80 ℃;
(4) weighing the dried PC, PBT, the compound flame retardant and the ester exchange inhibitor according to the weight ratio, adding the mixture into a high-speed mixer, uniformly mixing, adding the conductive master batch, the low-temperature-resistant toughening agent, the dispersing agent, the solubilizer and the antioxidant according to the mass ratio, and fully mixing for 3 minutes;
(5) and adding the mixed materials into a double-screw extruder for full melt blending, controlling the melting temperature at 210 ℃ and the rotating speed of the screw at 500 rpm, and extruding and granulating through the double-screw extruder to obtain the low-temperature-resistant antistatic flame-retardant PC/PBT alloy material.
The main technical indexes of the PC/PBT alloy prepared by the 4 embodiments are shown in the following table 1:
table 1 examples 1 to 4 technical indices
Melt drop number index: and horizontally clamping a sample strip on a flame with the height of 2-3 cm continuously, burning, and calculating the number of molten drops within 1min, wherein the size of the sample strip is 60mm multiplied by 8mm multiplied by 4 mm.
From the comparison of the above examples 1 to 4 of the PC/PBT alloy, when the mass percentage ratio of PC is gradually increased and the mass percentage ratio of PBT is gradually decreased, the mass percentage ratio of the conductive master batch is gradually increased, the mass percentage ratio of the composite flame retardant is gradually decreased, and the mass percentage ratio of the low temperature resistant toughening agent is gradually increased within the limited range of the optimized ratio range of the matrix PC and the modified resin matrix PBT, the obtained test data are as shown in the above table: the melt index data becomes smaller;
comparing the examples 1 and 2, along with the increase of the mass percentage ratio of the PC to the low temperature resistant toughening agent and the decrease of the mass percentage ratio of the PBT to the compound flame retardant, the values of three test parameters of tensile strength, bending strength and bending modulus are all reduced greatly, and it can be known that when the mass percentage ratio of the PC to the low temperature resistant toughening agent is small, the influence of the three parameter values of the tensile strength, the bending strength and the bending modulus on the mass percentage ratio of the PBT to the compound flame retardant is large;
comparing example 2, example 3 and example 1, with the increase of the mass percentage ratio of the PC to the conductive master batch, the mass percentage ratio of the PBT to the compound flame retardant is reduced, and the values of three test parameters of tensile strength, bending strength and bending modulus are all increased from small to large, while the test values in example 3 are all larger than the test values in example 1, and it is known that with the increase of the mass percentage ratio of the PC and the mass percentage ratio of the PBT to the compound flame retardant is reduced, because the mass percentage ratio of the conductive master batch is increased, the tensile strength, bending strength and bending modulus are all gradually enhanced with the increase of the mass percentage ratio of the conductive master batch, and the properties of the tensile strength, bending strength and bending modulus of the PC/PBT alloy are all gradually enhanced.
Comparing examples 3 and 4 with examples 1 and 2, the mass percent ratio of PBT is decreased with the increase of the mass percent ratio of PC, the mass percent ratio of the composite flame retardant is continuously decreased, and the tensile strength, the flexural strength and the flexural modulus of the PC/PBT alloy are measured to be gradually increased, so that the PC/PBT alloy reaches (10-5):1, after the mass percentage ratio of the conductive master batch to the low-temperature resistant toughening agent is gradually increased, the mass ratio range of the conductive master batch to the total mass of the PC and the PBT is 1: (8-12), the influence on three performance parameters of tensile strength, bending strength and bending modulus is relatively limited, and the performance of the PC/PBT alloy is enhanced by further increasing the tensile strength, the bending strength and the bending modulus by reducing the mass percentage ratio of the compound flame retardant, the mass percentage ratio range of the compound flame retardant consisting of TPP and BDP is defined as 100 percent to 300 percent, when the mass percentage ratio is preferably 300%, in example 4, by comparing the tensile strength, the flexural strength and the flexural modulus of the PC/PBT alloy, except that the tensile strength, the flexural strength and the flexural modulus of the PC/PBT alloy are gradually increased to the maximum, and the performances reflected by the test values of the notch impact strength at normal temperature, the notch impact strength at-40 ℃, the flame retardance and the surface resistance of the PC/PBT alloy are gradually enhanced.
According to the embodiment, the low-temperature-resistant flame-retardant antistatic polycarbonate/polybutylene terephthalate (PC/PBT) alloy material has the advantages of dimensional stability, good heat resistance, high flame retardance, capability of enabling vertical combustion to reach UL94V-0 level, environmental friendliness, high low-temperature notch impact strength, good antistatic effect and surface resistivity of 106To 1010Omega · m and good surface gloss.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto, and variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the present invention.
Claims (10)
1. The low-temperature-resistant flame-retardant antistatic PC/PBT alloy is characterized by comprising the following components in percentage by mass:
the conductive master batch comprises 60 to 70 percent of carrier, 20 to 30 percent of carbon nano tube and 5 to 10 percent of pentaerythritol stearate according to mass percentage.
2. The low temperature resistant flame retardant antistatic PC/PBT alloy according to claim 1, wherein the conductive masterbatch further comprises superconducting carbon black, wherein the mass percentages are 60% to 65% of the carrier, 5% of the carbon nanotube, 20% to 25% of the superconducting carbon black, and 5% to 10% of pentaerythritol stearate, respectively.
3. The low temperature resistant flame retardant antistatic PC/PBT alloy according to claim 2, wherein the carrier is selected from thermoplastic resins.
4. The low-temperature-resistant flame-retardant antistatic PC/PBT alloy according to claim 3, wherein the mass percentages of the carrier, the carbon nanotubes, the superconducting carbon black and the pentaerythritol stearate in the conductive master batch are 65%, 5%, 25% and 5%, and the carrier is specifically polycarbonate.
5. The low-temperature-resistant flame-retardant antistatic PC/PBT alloy according to claim 1, wherein the compound flame retardant is prepared by compounding at least two of decabromodiphenyl ether, decabromodiphenyl ethane, triphenyl phosphate (TPP), bisphenol A-Bis Diphenyl Phosphate (BDP) or diethyl aluminum hypophosphite (ADP) according to mass equal proportion.
6. The low-temperature-resistant flame-retardant antistatic PC/PBT alloy according to claim 5, wherein the compound flame retardant is triphenyl phosphate and bisphenol A-bis diphenyl phosphate;
the low-temperature resistant toughening agent is methyl methacrylate-butadiene-styrene terpolymer (MBS);
the dispersant is at least one of stearic acid, OP wax or ethylene bis stearamide (MBS);
the ester exchange inhibitor is selected from at least one of sodium dihydrogen phosphate, disodium dihydrogen pyrophosphate, triphenyl phosphite or sodium acid pyrophosphate (SAPP).
7. The low temperature resistant flame retardant antistatic PC/PBT alloy according to claim 1, wherein the solubilizer is ethylene-methyl acrylate-glycidyl methacrylate terpolymer (E-MA-GMA).
8. The low-temperature-resistant flame-retardant antistatic PC/PBT alloy according to claim 1, wherein the antioxidant is a compound of hindered phenol antioxidant 1010 and phosphite antioxidant 168 in equal proportion.
9. The preparation method of the low-temperature-resistant flame-retardant antistatic PC/PBT alloy is characterized by comprising the following steps of:
drying PC at 120-130 deg.C for 3-4 hr to make its water content below 0.02;
drying PBT at 120-140 deg.C for 3-4 hr to make its water content below 0.03;
weighing at least two of decabromodiphenyl ether, decabromodiphenyl ethane, triphenyl phosphate, bisphenol A-bis (diphenyl phosphate) or diethyl aluminum hypophosphite according to the equal weight proportion, mixing, stirring for 1 to 3 minutes, uniformly mixing, and drying the mixture for 30 to 50 minutes at 50 to 80 ℃;
weighing 30-78% of dried PC, 5-30% of PBT, 5-20% of compound flame retardant and 0.3-3% of ester exchange inhibitor according to weight percentage, and uniformly mixing; then adding 5 to 30 percent of conductive master batch, 5 to 20 percent of low temperature resistant toughening agent, 0.5 to 2 percent of dispersing agent, 0.5 to 3 percent of solubilizer and 0.4 to 1 percent of antioxidant which are weighed according to the weight percentage, and fully mixing for 3 to 5 minutes;
and adding the mixed materials into a double-screw extruder to be fully melted and blended, wherein the melting temperature is 210-260 ℃, the rotating speed of the screw is 300-500 r/min, and extruding and granulating through the double-screw extruder to obtain the low-temperature-resistant antistatic flame-retardant PC/PBT alloy material.
10. The preparation method of the low-temperature-resistant flame-retardant antistatic PC/PBT alloy according to claim 9, wherein the conductive master batch is prepared by the following steps: weighing 60-65% of carrier, 5% of carbon nano tube, 20-25% of superconducting carbon black and 5-10% of pentaerythritol stearate according to the mass percentage, carrying out melt blending in preparation equipment at 210-220 ℃, and granulating through a granulator, wherein in the mixing process, the carbon nano tube is added for multiple times.
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