CN109880317B - Glass fiber reinforced halogen-free flame-retardant PCT material and preparation method thereof - Google Patents
Glass fiber reinforced halogen-free flame-retardant PCT material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of flame-retardant materials, in particular to a glass fiber reinforced halogen-free flame-retardant PCT material and a preparation method thereof. The glass fiber reinforced halogen-free flame retardant PCT material comprises the following raw materials in parts by weight: 80-100 parts of PCT resin, 15-25 parts of PCTG resin, 8-10 parts of halogen-free flame retardant A, 1-4 parts of halogen-free flame retardant B, 10-15 parts of heat absorbent, 0.2-0.6 part of antioxidant, 0.2-0.6 part of heat stabilizer, 0.2-0.6 part of lubricant and 35-45 parts of glass fiber; the halogen-free flame retardant A is diethyl aluminum phosphinate, and the halogen-free flame retardant B is at least one of melamine cyanurate and melamine polyphosphate. The flame retardance can reach 0.8mmV-0 level, the reflow soldering temperature can reach 270 ℃ for 30s, and yellowing and bubbling are avoided.
Description
Technical Field
The invention relates to the technical field of flame-retardant materials, in particular to a glass fiber reinforced halogen-free flame-retardant PCT material and a preparation method thereof.
Background
Because of the requirement of environmental protection, wave soldering is gradually replaced by reflow soldering, and the soldering mode gradually changes from lead soldering to lead-free soldering, but the soldering temperature of the lead-free soldering is higher than that of the lead soldering, so the soldering tin temperature resistance requirement of the material is correspondingly improved. The solder-resisting temperature of the connector in the current market is about 265 ℃, the traditional materials such as PBT, PET, PA66 and the like can not meet the requirement of high-temperature solder, and PA6T can resist temperature, but is easy to yellow and bubble.
In view of the fact that after electronic waste materials and plastic products containing halogen compounds are burnt, century toxic Dioxin (Dioxin) compounds are easily generated, and the health hazard is caused by biological accumulation. International companies such as: apple, DELL, etc. successively promulgate the halogen-free requirement specification at the end of 2006, clearly defining that the products do not contain halogen (bromine, chlorine) related substances. Apple's restriction on halogens is IEC 61249-2-21: the 2003 standard is based. According to IEC standards, halogen limitations apply to chlorine (Cl) and bromine (Br). In view of the demand of market for non-halogenation, halogen-free flame retardant materials have been widely used in electronic and electric products, especially in electronic consumer products which are often contacted by human bodies.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the glass fiber reinforced halogen-free flame retardant PCT material, which has flame retardance reaching 0.8mmV-0 level, reflow soldering temperature resistance reaching 270 ℃ for 30s, no yellowing and no foaming.
The second purpose of the invention is to provide a preparation method of the glass fiber reinforced halogen-free flame retardant PCT material, which has the advantages of simple preparation steps, controllable conditions and high preparation efficiency, and is suitable for large-scale industrial production.
The first purpose of the invention is realized by the following technical scheme: the glass fiber reinforced halogen-free flame retardant PCT material comprises the following raw materials in parts by weight:
the halogen-free flame retardant A is diethyl aluminum phosphinate, and the halogen-free flame retardant B is at least one of melamine cyanurate and melamine polyphosphate.
By adopting the raw materials in parts by weight and types, the prepared composite material has excellent flame retardant property, high tensile strength, impact strength and thermal stability, the flame retardant property can reach 0.8mmV-0 level, the reflow soldering resistance temperature can reach 265 ℃ for 30s, and the composite material is not yellowed and foamed.
The invention blends PCT resin with good toughness, thermal stability, easy processability, chemical resistance and low hygroscopicity and PCTG resin with high impact resistance, radiation resistance and excellent chemical resistance, and adds glass fiber to reinforce and modify the matrix of the composite resin, so that the prepared composite material has good mechanical properties and thermal stability such as impact resistance, high tensile strength and the like, the composite material does not generate yellowing and bubbling, and the cost of the composite material is 25-50% lower than that of the composite material taking high-temperature engineering materials such as PA9T, PA10T, LCP and the like as matrix resin.
The heat absorbent is added to carry out the synergistic interaction with the halogen-free flame retardant A and the halogen-free flame retardant B to compound the flame retardant property of the composite material, and the heat absorbent passes through the halogen-free flame retardant A and the halogen-free flame retardant B when the composite material is heated or combustedThe heat absorption performance reduces the temperature of a system, the spread of fire is delayed, the diethyl aluminum phosphinate mainly generates a flame retardant effect through a gas phase, the diethyl aluminum phosphinate is decomposed into diethyl phosphinic acid and is volatilized to the gas phase in the combustion process, and the combustion is inhibited by capturing free radicals generated by the combustion; and the melamine cyanurate and the melamine polyphosphate of the halogen-free flame retardant B are decomposed into volatile CO2 and NH3And the gases generate flame retardance through the fuel dilution effect, and the heat absorbing agent, the halogen-free flame retardant A and the halogen-free flame retardant B generate flame retardance through different mechanisms to generate a synergistic flame retardant effect. The flame retardant is compounded, when the addition amount of the flame retardant accounts for less than 10% of the mass fraction of the composite material, the flame retardant property of the prepared composite material can reach 0.8mmV-0 level, and the production cost is effectively reduced. The addition of the heat stabilizer can improve the thermal stability of the prepared composite material, so that the prepared composite material is not easy to deform when being heated, and simultaneously can improve the thermal stability of the antioxidant, so that the antioxidant added into the composite material is not easy to volatilize when the composite material is heated, and the aging resistance and the thermal stability of the composite material are improved under the synergistic effect of the antioxidant and the antioxidant.
Specifically, the PCT resin with the intrinsic viscosity of 0.8dL/g and the lubricant are adopted, so that the processing fluidity and the toughness of the composite material are improved, and the prepared composite material has high impact resistance, smooth surface and high glossiness.
The antioxidant is at least one of 1010, 1098 and 1076.
The heat stabilizer is a mixture of S9228 and dihydropyridine in a weight ratio of 3: 0.5-1.
The common antioxidant is easy to volatilize at high temperature and is not suitable for being applied to a reflow soldering process, the antioxidant 1010, the antioxidant 1098 and the antioxidant 1076 are compounded by adopting the antioxidant and the composite heat stabilizer, the high temperature resistance of the antioxidant is improved, the ageing resistance, the high temperature resistance, the flame retardant property and the mechanical property of the composite material are improved, and the prepared composite material is not yellowed and foamed.
The lubricant is at least one of silicone powder, montan wax and pentaerythritol stearate.
The addition of the lubricant improves the compatibility and the adhesive force of each raw material component and the composite resin, and simultaneously improves the impregnation property, the dispersibility and the fluidity of the glass fiber, thereby improving the flame retardant property and the tensile strength of the product.
The glass fiber is chopped glass fiber with monofilament diameter of 9-11 μm.
The chopped glass fibers with the diameters have better compatibility with the composite resin and other raw material components, and are favorable for improving the dispersibility and the flowability of the raw material components in the composite resin and improving the flame retardant property and the tensile strength of the composite material. When the diameter of the glass fiber is too large, the prepared composite material has large surface roughness and high reject ratio.
The preparation method of the endothermic agent comprises the following steps:
A. neutralizing 40-60 parts by weight of acrylic acid with 80-100 parts by weight of 35-40 wt% sodium hydroxide solution, adding 10-15 parts by weight of acrylamide, uniformly stirring, cooling to room temperature, adding 0.1-0.5 part by weight of N, N-methylene bisacrylamide, fully stirring and dissolving, introducing nitrogen to remove oxygen, and preparing a polymerization solution;
B. uniformly mixing 5-8 parts by weight of cyclohexane and 0.5-3 parts by weight of Span-80, adding the polymerization solution prepared in the step A, heating to 35-40 ℃, adding 15-20 parts by weight of ammonium persulfate-sodium sulfite, reacting for 0.5-1h, performing suction filtration, drying and grinding to obtain sodium polyacrylate water-absorbent resin particles;
C. and B, mixing the sodium polyacrylate water-absorbent resin particles prepared in the step B and water according to a weight ratio of 1: 5-10, and the sodium polyacrylate water-absorbent resin particles absorb water and swell;
D. and C, mixing 25-50 parts by weight of polypropylene resin with the sodium polyacrylate water-absorbent resin particles after water absorption in the step C, and putting the mixture into extrusion equipment for melt extrusion to prepare the heat absorbent.
According to the invention, the polypropylene resin is coated on the outer surface of the sodium polyacrylate water-absorbent resin particles after water absorption expansion by adopting the preparation method, so that the heat absorbent with the core-shell structure, which takes the sodium polyacrylate water-absorbent resin particles after water absorption expansion as a core and takes the polypropylene resin as a shell, is formed. When the composite material is heated and combusted, the water absorbed in the sodium polyacrylate water-absorbing resin absorbs heat and is gasified, so that the temperature is reduced, the fire spread is delayed, and the purpose of improving the flame retardant property of the resin matrix is achieved. And the polypropylene resin is wrapped on the outer surface of the sodium polyacrylate water-absorbent resin particles, so that the hygroscopicity of the sodium polyacrylate water-absorbent resin particles is reduced, and the sodium polyacrylate water-absorbent resin particles added in the composite material can not adsorb moisture in the environment and continue to expand to cause the phenomenon that the surface of the composite material is uneven. According to the invention, the cross-linking degree of the prepared water-absorbent resin is further controlled by controlling the weight ratio of sodium hydroxide, acrylic acid, acrylamide and N, N-methylene bisacrylamide, when the content of N, N-methylene bisacrylamide is too large, the cross-linking degree of the prepared water-absorbent resin is too high, and the water absorption performance cannot meet the water absorption requirement of the invention, and when the content of N, N-methylene bisacrylamide is too small, the prepared water-absorbent resin has low gel strength and is easy to absorb moisture and coagulate.
The first zone temperature of the extrusion device in the step D is 175-190 ℃, the second zone temperature is 180-210 ℃, the third zone temperature is 190-210 ℃, the fourth zone temperature is 210-230 ℃, and the fifth zone temperature is 210-230 ℃.
According to the invention, the temperature of each zone of the extrusion equipment is controlled, so that the polypropylene resin can be better coated on the surface of the sodium polyacrylate water-absorbent resin particles after water absorption expansion to form a core-shell structure, when the temperature is too low or too high, the polypropylene resin can be caused to be incapable of being completely coated on the surface of the sodium polyacrylate water-absorbent resin particles after water absorption expansion or be easily separated from the water-absorbent resin particles during later processing, and the water-absorbent resin particles can easily absorb moisture to expand to cause the surface unevenness of the composite material.
And the particle size of the sodium polyacrylate water-absorbent resin particles prepared in the step B is 50-150 nm.
When the particle size of the sodium polyacrylate water-absorbent resin particles is too large, the surface of the prepared composite material is uneven and has higher roughness, and when the particle size is too small, the sodium polyacrylate water-absorbent resin particles cannot effectively absorb enough water, so that the heat absorption and cooling performance of the composite material is influenced, and the flame retardant performance of the composite material is reduced.
According to the preparation method of the glass fiber reinforced halogen-free flame retardant PCT material, the PCT resin, the PCTG resin, the halogen-free flame retardant A, the halogen-free flame retardant B, the antioxidant, the heat stabilizer, the lubricant, the glass fiber and the heat absorbent are mixed and uniformly stirred according to the weight ratio of the components, and then the mixed material is put into an extrusion device for melt extrusion and granulation to prepare the glass fiber reinforced halogen-free flame retardant PCT material.
The stirring speed of the mixing and stirring is 900-1000r/min, the temperature of the first zone of the extrusion equipment is 180-200 ℃, the temperature of the second zone is 210-230 ℃, the temperature of the third zone is 220-240 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-250 ℃, the temperature of the sixth zone is 240-260 ℃, the temperature of the seventh zone is 240-260 ℃, the temperature of the eighth zone is 230-250 ℃, and the temperature of the ninth zone is 230-250 ℃.
According to the invention, by controlling the temperature of each zone in the extrusion equipment, the prepared composite material has excellent flame retardant property, thermal stability, high tensile strength and high impact strength, does not turn yellow or foam, and has a smooth surface and high glossiness. When the temperature of each zone is too high, the subsequent heat absorption effect of the heat absorbent is influenced, and the flame retardant property, the thermal stability and the tensile property of the prepared composite material are further reduced.
The invention has the beneficial effects that:
1. by adopting the raw materials in parts by weight and types, the prepared composite material has excellent flame retardant property, high tensile strength, impact strength and better thermal stability, the flame retardant property can reach 0.8mmV-0 level, the reflow soldering temperature can reach 265 ℃ and 30s, and the composite material is not yellowed and foamed;
2. according to the invention, sodium polyacrylate water-absorbing resin particles after water absorption expansion are added into the composite material as a core, polypropylene resin is used as a heat-absorbing agent with a core-shell structure of a shell, the heat-absorbing agent, the halogen-free flame retardant A and the halogen-free flame retardant B have a synergistic effect, when the composite material is heated and combusted, water absorbed in the heat-absorbing agent absorbs heat and is gasified, the ambient temperature is reduced, the fire spread is delayed, the halogen-free flame retardant A diethyl aluminum phosphinate mainly generates a flame-retardant effect through a gas phase, the diethyl aluminum phosphinate is decomposed into diethyl phosphinic acid to be volatilized to the gas phase in the combustion process, and the combustion is inhibited by capturing free radicals generated by the combustion; the melamine cyanurate and the melamine polyphosphate of the halogen-free flame retardant B are decomposed into volatile gases such as CO2 and NH3, flame retardance is generated through the fuel dilution effect, the heat absorbent, the halogen-free flame retardant A and the halogen-free flame retardant B generate flame retardance through different mechanisms to generate a synergistic flame retardant effect, the three are compounded, and the flame retardant property of the prepared composite material can reach 0.8mmV-0 grade when the addition amount of the flame retardant accounts for less than 10% of the mass fraction of the composite material, so that the production cost is effectively reduced.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
The glass fiber reinforced halogen-free flame retardant PCT material comprises the following raw materials in parts by weight:
the halogen-free flame retardant A is diethyl aluminum phosphinate, and the halogen-free flame retardant B is melamine cyanurate. The lubricant is silicone powder. The glass fiber is chopped glass fiber with monofilament diameter of 10 mu m. The intrinsic viscosity of the PCT resin is 0.8 dL/g. The heat stabilizer is a mixture of S9228 and dihydropyridine in a weight ratio of 3:0.75
The preparation method of the endothermic agent comprises the following steps:
A. neutralizing 50 parts by weight of acrylic acid with 90 parts by weight of 37.5 wt% sodium hydroxide solution, adding 12.5 parts by weight of acrylamide, uniformly stirring, cooling to room temperature, adding 0.3 part by weight of N, N-methylene bisacrylamide, fully stirring and dissolving, introducing nitrogen to remove oxygen, and preparing a polymerization solution;
B. uniformly mixing 6.5 parts by weight of cyclohexane and 1.75 parts by weight of Span-80, adding the polymerization solution prepared in the step A, heating to 37.5 ℃, adding 17.5 parts by weight of ammonium persulfate-sodium sulfite, reacting for 0.75h, performing suction filtration, drying and grinding to obtain sodium polyacrylate water-absorbent resin particles with the particle size of 100 nm;
C. and B, mixing the sodium polyacrylate water-absorbent resin particles prepared in the step B and water according to a weight ratio of 1: 7.5, mixing, and allowing the sodium polyacrylate water-absorbent resin particles to absorb water and expand;
D. and C, mixing 32.5 parts by weight of polypropylene resin with the sodium polyacrylate water-absorbent resin particles after water absorption in the step C, and putting the mixture into extrusion equipment for melt extrusion to prepare the heat absorbent.
The first zone temperature of the extrusion device in the step D is 183 ℃, the second zone temperature is 195 ℃, the third zone temperature is 200 ℃, the fourth zone temperature is 220 ℃ and the fifth zone temperature is 220 ℃.
According to the preparation method of the glass fiber reinforced halogen-free flame retardant PCT material, the PCT resin, the PCTG resin, the halogen-free flame retardant A, the halogen-free flame retardant B, the antioxidant 1010, the heat stabilizer, the lubricant, the glass fiber and the heat absorbent are mixed and uniformly stirred according to the weight ratio of the components, and then the mixed material is put into an extrusion device for melt extrusion and granulation to prepare the glass fiber reinforced halogen-free flame retardant PCT material.
The stirring speed of the mixing and stirring is 950r/min, the temperature of the first zone of the extrusion equipment is 190 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 230 ℃, the temperature of the fourth zone is 240 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 240 ℃, and the temperature of the ninth zone is 240 ℃.
Example 2
The glass fiber reinforced halogen-free flame retardant PCT material comprises the following raw materials in parts by weight:
the halogen-free flame retardant A is diethyl aluminum phosphinate, and the halogen-free flame retardant B is melamine sodium polyphosphate. The lubricant is montan wax. The glass fiber is chopped glass fiber with the monofilament diameter of 9 mu m. The intrinsic viscosity of the PCT resin is 0.8 dL/g. The heat stabilizer is a mixture of S9228 and dihydropyridine in a weight ratio of 3: 0.5.
The preparation method of the endothermic agent comprises the following steps:
A. neutralizing 40 parts by weight of acrylic acid with 80 parts by weight of 35 wt% sodium hydroxide solution, adding 10 parts by weight of acrylamide, uniformly stirring, cooling to room temperature, adding 0.1 part by weight of N, N-methylene bisacrylamide, fully stirring and dissolving, introducing nitrogen to remove oxygen, and preparing a polymerization solution;
B. uniformly mixing 5 parts by weight of cyclohexane and 0.5 part by weight of Span-80, adding the polymerization solution prepared in the step A, heating to 35 ℃, adding 15 parts by weight of ammonium persulfate-sodium sulfite, reacting for 0.5h, performing suction filtration, drying and grinding to obtain sodium polyacrylate water-absorbent resin particles with the particle size of 50 nm;
C. and B, mixing the sodium polyacrylate water-absorbent resin particles prepared in the step B and water according to a weight ratio of 1: 5, mixing, and allowing the sodium polyacrylate water-absorbent resin particles to absorb water and swell;
D. and C, mixing 25 parts by weight of polypropylene resin with the sodium polyacrylate water-absorbent resin particles after water absorption in the step C, and putting the mixture into extrusion equipment for melt extrusion to prepare the heat absorbent.
The first zone temperature of the extrusion device in the step D is 175 ℃, the second zone temperature is 180 ℃, the third zone temperature is 190 ℃, the fourth zone temperature is 210 ℃ and the fifth zone temperature is 210 ℃.
According to the preparation method of the glass fiber reinforced halogen-free flame retardant PCT material, the PCT resin, the PCTG resin, the halogen-free flame retardant A, the halogen-free flame retardant B, the antioxidant 1098, the heat stabilizer, the lubricant, the glass fiber and the heat absorbent are mixed and stirred uniformly according to the weight ratio of the components, and then the mixed material is put into an extrusion device for melt extrusion and granulation to prepare the glass fiber reinforced halogen-free flame retardant PCT material.
The stirring speed of the mixing and stirring is 900r/min, the temperature of the first zone of the extrusion equipment is 180 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 230 ℃, the temperature of the sixth zone is 240 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 230 ℃, and the temperature of the ninth zone is 230 ℃.
Example 3
The glass fiber reinforced halogen-free flame retardant PCT material comprises the following raw materials in parts by weight:
the halogen-free flame retardant A is diethyl aluminum phosphinate, and the halogen-free flame retardant B is melamine cyanurate. The lubricant is pentaerythritol stearate. The glass fiber is chopped glass fiber with monofilament diameter of 11 mu m. The intrinsic viscosity of the PCT resin is 0.8 dL/g. The heat stabilizer is a mixture of S9228 and dihydropyridine in a weight ratio of 3: 1.
The preparation method of the endothermic agent comprises the following steps:
A. neutralizing 60 parts by weight of acrylic acid with 100 parts by weight of 40 wt% sodium hydroxide solution, adding 15 parts by weight of acrylamide, uniformly stirring, cooling to room temperature, adding 0.5 part by weight of N, N-methylene bisacrylamide, fully stirring and dissolving, introducing nitrogen to remove oxygen, and preparing a polymerization solution;
B. uniformly mixing 8 parts by weight of cyclohexane and 3 parts by weight of Span-80, adding the polymerization solution prepared in the step A, heating to 40 ℃, adding 20 parts by weight of ammonium persulfate-sodium sulfite, reacting for 1 hour, performing suction filtration, drying and grinding to obtain sodium polyacrylate water-absorbent resin particles with the particle size of 150 nm;
C. and B, mixing the sodium polyacrylate water-absorbent resin particles prepared in the step B and water according to a weight ratio of 1: 10, mixing, and allowing the sodium polyacrylate water-absorbent resin particles to absorb water and swell;
D. and C, mixing 50 parts by weight of polypropylene resin with the sodium polyacrylate water-absorbent resin particles after water absorption in the step C, and putting the mixture into extrusion equipment for melt extrusion to prepare the heat absorbent.
The temperature of the first zone, the temperature of the second zone, the temperature of the third zone, the temperature of the fourth zone and the temperature of the fifth zone of the extrusion equipment in the step D are respectively 190 ℃, 210 ℃, 230 ℃ and 230 ℃.
According to the preparation method of the glass fiber reinforced halogen-free flame retardant PCT material, the PCT resin, the PCTG resin, the halogen-free flame retardant A, the halogen-free flame retardant B, the antioxidant, the heat stabilizer, the lubricant, the glass fiber and the heat absorbent are mixed and uniformly stirred according to the weight ratio of the components, and then the mixed material is put into an extrusion device for melt extrusion and granulation to prepare the glass fiber reinforced halogen-free flame retardant PCT material.
The stirring speed of the mixing and stirring is 1000r/min, the temperature of the first zone of the extrusion equipment is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 240 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 260 ℃, the temperature of the eighth zone is 250 ℃ and the temperature of the ninth zone is 250 ℃.
Example 4
Example 4 differs from example 1 in that example 4 does not add a thermal stabilizer.
Comparative example 1
Comparative example 1 differs from example 1 in that comparative example 1 does not add an endothermic agent.
Comparative example 2
Comparative example 2 differs from example 1 in that comparative example 2 does not add halogen-free flame retardant a.
Comparative example 3
Comparative example 3 is different from example 1 in that comparative example 3 does not add an endothermic agent, and comparative example 3 adds 16 parts by weight of a polypropylene resin.
Performance testing
The glass fiber reinforced halogen-free flame retardant PCT materials prepared in the above examples 1-4 and comparative examples 1-3 were respectively tested for impact resistance, flame retardancy, tensile strength, heat distortion temperature, etc., wherein the flame retardancy test standard is UL94, the impact resistance test standard is ISO180, the tensile strength test standard is ISO527, and the heat distortion temperature test standard is ISO75-2, and the test results are shown in the following table.
As shown in the table, the flame retardant grade of the glass fiber reinforced halogen-free flame retardant PCT material is 0.8mmV-0 grade, the thermal deformation temperature is 260-270 ℃, the flame retardant property is good, the thermal stability is good, and the impact strength is 13-15kJ/m2The tensile strength is between 132 and 140MPa, and the mechanical property is excellent. The appearance of the prepared glass fiber reinforced halogen-free flame retardant PCT material is observed, so that the prepared glass fiber reinforced flame retardant PCT material has the advantages of smooth surface, high glossiness, no yellowing phenomenon and no foaming phenomenon, and is suitable for being used in a reflow soldering process.
As can be seen by comparing the embodiment 1 and the embodiment 4, the addition of the antioxidant 1010, the heat stabilizer S9228 and the dihydropyridine have a synergistic effect, and the heat deformation temperature and the mechanical property of the glass fiber reinforced halogen-free flame retardant PCT material are improved by compounding the antioxidant 1010, the heat stabilizer S9228 and the dihydropyridine.
As can be seen by comparing the example 1 with the comparative example 1 and the comparative example 2, the flame retardant property, the impact resistance and the tensile strength of the composite material can be effectively improved by adding the heat absorbent, the halogen-free flame retardant A and the halogen-free flame retardant B.
As can be seen from comparison between example 1 and comparative example 1 with comparative example 3, the addition of the heat absorbent of the present invention is more beneficial to improving the impact resistance of the composite material than the addition of polypropylene resin in equal parts by weight.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (7)
1. The glass fiber reinforced halogen-free flame-retardant PCT material is characterized by comprising the following components in parts by weight: the feed comprises the following raw materials in parts by weight:
the halogen-free flame retardant A is diethyl aluminum phosphinate, and the halogen-free flame retardant B is at least one of melamine cyanurate and melamine polyphosphate;
the preparation method of the endothermic agent comprises the following steps:
A. neutralizing 40-60 parts by weight of acrylic acid with 80-100 parts by weight of 35-40 wt% sodium hydroxide solution, adding 10-15 parts by weight of acrylamide, uniformly stirring, cooling to room temperature, adding 0.1-0.5 part by weight of N, N-methylene bisacrylamide, fully stirring and dissolving, introducing nitrogen to remove oxygen, and preparing a polymerization solution;
B. uniformly mixing 5-8 parts by weight of cyclohexane and 0.5-3 parts by weight of Span-80, adding the polymerization solution prepared in the step A, heating to 35-40 ℃, adding 15-20 parts by weight of ammonium persulfate-sodium sulfite, reacting for 0.5-1h, performing suction filtration, drying and grinding to obtain sodium polyacrylate water-absorbent resin particles;
C. and B, mixing the sodium polyacrylate water-absorbent resin particles prepared in the step B and water according to a weight ratio of 1: 5-10, and the sodium polyacrylate water-absorbent resin particles absorb water and swell;
D. mixing 25-50 parts by weight of polypropylene resin with the sodium polyacrylate water-absorbent resin particles after water absorption in the step C, and putting the mixture into extrusion equipment for melt extrusion to prepare the heat absorbent;
the first zone temperature of the extrusion equipment in the step D is 175-190 ℃, the second zone temperature is 180-210 ℃, the third zone temperature is 190-210 ℃, the fourth zone temperature is 210-230 ℃, and the fifth zone temperature is 210-230 ℃;
and the particle size of the sodium polyacrylate water-absorbent resin particles prepared in the step B is 50-150 nm.
2. The glass fiber reinforced halogen-free flame retardant PCT material as claimed in claim 1, wherein: the antioxidant is at least one of 1010, 1098 and 1076.
3. The glass fiber reinforced halogen-free flame retardant PCT material as claimed in claim 1, wherein: the heat stabilizer is a mixture of S9228 and dihydropyridine in a weight ratio of 3: 0.5-1.
4. The glass fiber reinforced halogen-free flame retardant PCT material as claimed in claim 1, wherein: the lubricant is at least one of silicone powder, montan wax and pentaerythritol stearate.
5. The glass fiber reinforced halogen-free flame retardant PCT material as claimed in claim 1, wherein: the glass fiber is chopped glass fiber with monofilament diameter of 9-11 μm.
6. A method for preparing the glass fiber reinforced halogen-free flame retardant PCT material as claimed in any one of claims 1 to 5, characterized in that: according to the weight ratio of the components, mixing and uniformly stirring the PCT resin, the PCTG resin, the halogen-free flame retardant A, the halogen-free flame retardant B, the antioxidant, the heat stabilizer, the lubricant, the glass fiber and the heat absorbent, then putting the mixed material into an extrusion device for melt extrusion and granulation to prepare the glass fiber reinforced halogen-free flame retardant PCT material.
7. The preparation method of the glass fiber reinforced halogen-free flame retardant PCT material according to claim 6, which is characterized in that: the stirring speed of the mixing and stirring is 900-1000r/min, the temperature of the first zone of the extrusion equipment is 180-200 ℃, the temperature of the second zone is 210-230 ℃, the temperature of the third zone is 220-240 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-250 ℃, the temperature of the sixth zone is 240-260 ℃, the temperature of the seventh zone is 240-260 ℃, the temperature of the eighth zone is 230-250 ℃, and the temperature of the ninth zone is 230-250 ℃.
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| JPH06200132A (en) * | 1992-09-18 | 1994-07-19 | Toray Ind Inc | Resin composition for lamp reflector |
| US9074092B2 (en) * | 2010-12-20 | 2015-07-07 | Eastman Chemical Company | Miscible polyester blends utilizing recycled polyesters |
| KR102059493B1 (en) * | 2012-08-29 | 2019-12-26 | 에스케이케미칼 주식회사 | Non-halogen flame-retarding polycyclohexylenedimethyleneterephtalate resin composition |
| KR101849830B1 (en) * | 2015-06-30 | 2018-04-18 | 롯데첨단소재(주) | Polyester resin composition with excellent impact resistance and light reliability and molded article using the same |
| CN105623206B (en) * | 2016-03-09 | 2017-12-15 | 深圳华力兴新材料股份有限公司 | A kind of NMT polymer blends for possessing LDS functions |
| CN107189319B (en) * | 2017-05-16 | 2019-01-15 | 浙江大学 | Wire and cable full cloudy surface flexibility halogen-free flame-retardant thermoplastic elastomer PP Pipe Compound of high frosted and preparation method thereof |
| CN109370168A (en) * | 2018-10-17 | 2019-02-22 | 横店集团得邦工程塑料有限公司 | A kind of inorganic nano-particle enhancing flame-retardant PBT and preparation method thereof |
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