CN111363318B - Flame-retardant smoke-suppressing PTT polyester composite material and preparation method therefor - Google Patents
Flame-retardant smoke-suppressing PTT polyester composite material and preparation method therefor Download PDFInfo
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Abstract
The invention discloses a flame-retardant smoke-suppressing PTT polyester composite material and a preparation method thereof, which relate to the field of polyester preparation and comprise the following raw materials in parts by mass: 100 parts of PTT polyester, 5-80 parts of modified polyester, 5-50 parts of glass fiber, 10-30 parts of hydroxide-containing nano composite flame retardant, 5-30 parts of carbon forming agent, 1-30 parts of toughening agent, 1-30 parts of coupling agent, 0.1-1 part of antioxidant and 0.01-4 parts of nucleating agent. The invention uses the carbon forming agent and the nano composite flame retardant containing hydroxide in a matching way, not only can retard flame, but also reduces the generation of toxic smoke, plays a role of inhibiting smoke, and can take away a large amount of heat while generating white water mist without polluting the environment.
Description
Technical Field
The invention relates to the field of polyester preparation, in particular to a flame-retardant smoke-suppressing PTT polyester composite material and a preparation method thereof.
Background
PTT (polytrimethylene terephthalate) is a novel polyester with excellent performance in a polyester family, has a special 'odd carbon effect', has a unique spiral structure and very good elasticity, has the softness of nylon, the fluffiness of acrylic fibers and the dirt resistance and the antistatic property of terylene, and is widely applied to the fields of textile industry, decoration, engineering plastics and the like. In recent years, with the continuous development of blending technology, PTT polymer alloy products are receiving more and more attention, and are widely applied to electronics, electrical industry, automobile part industry, manufacturing industry and the like, and electronic and electrical products generally have higher requirements on flame retardant properties, such as flame retardance, molten drop resistance, smoke suppression and the like.
For example, chinese patents CN102888012A and CN202705585U disclose radiation crosslinking to prepare flame-retardant anti-dripping materials, but the process is complicated, radiation is harmful to human body, and the like, and thus the method is not suitable for industrial production. Chinese patent CN101225220B discloses a flame-retardant reinforced polybutylene terephthalate compound and a production method thereof, wherein the flame-retardant reinforced polybutylene terephthalate compound has good flame-retardant property and physical comprehensive property, but antimony trioxide is adopted as a flame retardant, so that the flame-retardant reinforced polybutylene terephthalate compound has the problem of heavy metal and does not have the smoke suppression function.
Disclosure of Invention
The invention provides a flame-retardant smoke-suppressing PTT polyester composite material and a preparation method thereof, aiming at overcoming the problems that the existing PTT polyester has poor flame-retardant effect, or the flame-retardant PTT polyester has complex preparation process and is not suitable for industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
the flame-retardant smoke-inhibiting PTT polyester composite material comprises the following raw materials in parts by mass: 100 parts of PTT polyester, 5-80 parts of modified polyester, 5-50 parts of glass fiber, 10-30 parts of hydroxide-containing nano composite flame retardant, 5-30 parts of carbon forming agent, 1-30 parts of toughening agent, 1-30 parts of coupling agent, 0.1-1 part of antioxidant and 0.01-4 parts of nucleating agent.
The invention adds the carbon forming agent and the hydroxide-containing nano composite flame retardant into the material of the PTT polyester composite material, wherein, the carbon forming agent can form an insulating layer, has stronger heat insulation and oxygen insulation capabilities, can prevent the burning of polyester under the action of matching with the nano composite flame retardant, however, because the polyester can not be burnt, higher heat accumulated in the polyester can not be released everywhere, at the moment, because the nano composite flame retardant comprises hydroxide, the hydroxide is heated and decomposed to absorb heat, white water mist is generated, the generation of toxic smoke is reduced, meanwhile, the oxygen content on the surface of the polyester material is reduced, and the polyester material can be self-contained, so that the flame retardant can not only resist flame by matching the carbon forming agent with the nano composite flame retardant containing hydroxide, meanwhile, the generation of toxic smoke is reduced, the smoke suppression effect is achieved, and the generated white water mist can take away a large amount of heat without polluting the environment.
Preferably, the nano composite flame retardant is obtained by compounding a main flame retardant and an auxiliary flame retardant in a mass ratio of 6-7: 4-3; the main flame retardant is zirconium phosphate, and the auxiliary flame retardant is obtained by compounding magnesium hydroxide and aluminum hydroxide according to the mass ratio of 1-1.2: 1.
Preferably, the preparation of the nanocomposite flame retardant comprises the following steps:
1) placing zirconium phosphate in ethylenediamine, wherein the molar ratio of amine to zirconium nNH3the/nZr is 40-50: 1; stirring for 24-48h at normal temperature, centrifuging, washing the precipitate with water and ethanol, drying and dispersing to obtain intercalation-treated zirconium phosphate;
2) pre-drying magnesium hydroxide and aluminum hydroxide at the temperature of 100-120 ℃, then placing the magnesium hydroxide and the aluminum hydroxide into a high-speed mixing stirrer, and uniformly stirring the magnesium hydroxide and the aluminum hydroxide at the temperature of 100-120 ℃ to prepare the secondary flame retardant;
3) and uniformly mixing the intercalated zirconium phosphate and the auxiliary flame retardant to prepare the nano composite flame retardant.
The nano composite flame retardant is obtained by compounding a main flame retardant and an auxiliary flame retardant, wherein the main flame retardant is a phosphorus flame retardant zirconium phosphate which has a layered mesoporous structure, after intercalation treatment, the spacing between layers is obviously increased, more polyester molecules can be accommodated, and the zirconium phosphate can be better dispersed in a polymer, and the auxiliary flame retardant is prepared by uniformly mixing the intercalated zirconium phosphate and the auxiliary flame retardant by adopting magnesium hydroxide and aluminum hydroxide which can be decomposed by heat.
Preferably, the surface of the nano composite flame retardant is subjected to organic coating treatment, and the method comprises the following coating steps:
a) placing the nano composite flame retardant into deionized water to prepare suspension, then heating to 65-85 ℃, adding a silicon source and an aqueous solution containing acid or alkali, aging for 1-2.5h, washing and drying to prepare the amorphous silicon dioxide coated nano composite flame retardant, wherein the thickness of the amorphous silicon dioxide is 1-15 nm;
b) placing the amorphous silicon dioxide coated nano composite flame retardant and the catalyst in an ethanol water solution, heating to 70-80 ℃, then dropwise adding 4-vinylbenzyl glycidyl ether, continuously stirring for reaction, returning to normal temperature after the reaction is finished, recovering the catalyst, and carrying out reduced pressure distillation to obtain the organic coated nano composite flame retardant.
The invention further carries out organic coating treatment on the surface of the nano composite flame retardant, firstly, the invention coats a layer of amorphous silicon dioxide on the surface of the nano composite flame retardant by a precipitation method, wherein the thickness of the amorphous silicon dioxide coating layer is 1-15nm, because the surface of the amorphous silicon dioxide has abundant hydroxyl groups, but the common silicon dioxide does not have the characteristics. After the surface of the nano composite flame retardant is coated with amorphous silicon dioxide rich in hydroxyl, 4-vinylbenzyl glycidyl ether is further grafted to the surface of the amorphous silicon dioxide coating of the nano composite flame retardant, because an epoxy group on the 4-vinylbenzyl glycidyl ether can perform a ring-opening reaction with the hydroxyl on the amorphous silicon dioxide under the action of a catalyst, so that the epoxy group is grafted to the surface of the amorphous silicon dioxide coating, and the organic coating nano composite flame retardant is prepared; at the moment, firstly, because the silicon dioxide has a flame-retardant enhancement effect, the flame retardance of the organically-coated nano composite flame retardant is enhanced, secondly, because the surface of the organically-coated nano composite flame retardant is provided with a unique benzene ring structure and a vinyl group, the organically-coated nano composite flame retardant has good compatibility with a PTT substrate and can be better dispersed in the substrate, and when the organically-coated nano composite flame retardant is burnt at high temperature, because the vinyl group on the surface of the organically-coated nano composite flame retardant is provided with double bonds, a physical-chemical cross-linking network structure can be formed by cross-linking at high temperature, the secondary scald caused by the melting and dropping of polyester due to heating is prevented, and the excellent anti-melting and dropping effect is achieved; and under the coordination of the nano composite flame retardant and the nitrogen-containing carbon forming agent, the nitrogen/phosphorus/silicon synergistic flame retardant effect is achieved, the formed silicon-carbon protective layer can improve the carbon forming rate and has stronger heat insulation and oxygen insulation capabilities, and therefore the flame retardant efficiency is improved.
Preferably, the concentration of the nanocomposite flame retardant in the suspension of step a) is 10 to 20 wt%.
Preferably, the mass ratio of the amorphous silica to the nanocomposite flame retardant is 5-20: 100.
Preferably, the catalyst in the step b) comprises resin-supported stannic chloride, and the mass of the catalyst is 1-2% of that of the organic-coated nano composite flame retardant.
Preferably, the modified polyester is one or more of PET, PETG, PCTG, Tritan modified polyester, PEN and PCCD; the toughening agent comprises one or more of maleic anhydride grafted ethylene-propylene-diene copolymer and maleic anhydride grafted styrene-butadiene-styrene copolymer; the nucleating agent comprises a compound of poly (ethylene-methacrylic acid) sodium salt and sodium stearate in a mass ratio of 1-1.2: 1; the coupling agent comprises a compound of KH550 and KH570 in a mass ratio of 1-1.2: 1; the antioxidant comprises a compound of 1010 and 168 in a mass ratio of 1-1.2: 1.
Preferably, the carbon forming agent comprises a nitrogen-containing carbon forming agent, and the nitrogen-containing carbon forming agent comprises ammonium polyphosphate.
A preparation method of a flame-retardant smoke-suppressing PTT polyester composite material comprises the following preparation steps:
s1) mixing the PTT, the modified polyester, the nano-composite flame retardant, the carbon forming agent, the toughening agent, the antioxidant, the nucleating agent and the coupling agent uniformly in a high-speed mixer;
s2) fully mixing the uniformly mixed raw materials with glass fibers through a double-screw extruder, and carrying out melting, extrusion, cooling, granulation and drying to obtain a product; wherein the double-screw extrusion process comprises the following steps: the 1-4 area is 235-; the screw rotation speed is 300-350 rpm/min.
Therefore, the invention has the following beneficial effects:
(1) according to the invention, the carbon forming agent and the nano composite flame retardant containing hydroxide are matched for use, so that the flame retardant can not only resist flame, but also reduce the generation of toxic smoke, and play a role in inhibiting smoke, and the generated white water mist can take away a large amount of heat while not polluting the environment;
(2) the organic coating nano composite flame retardant has a unique benzene ring structure and a vinyl group on the surface, so that the organic coating nano composite flame retardant has good compatibility with a PTT matrix and can be better dispersed in the matrix, and when the organic coating nano composite flame retardant is burnt at high temperature, the vinyl group on the surface of the organic coating nano composite flame retardant and the matrix form a cross-linked structure, so that a polyester molecular chain is in a cross-linked network state, a linear polymer is converted into a body polymer, secondary scald caused by melting and dropping of the polyester due to heating is prevented, and an excellent anti-melting and dropping effect is achieved; (3) under the coordination of the nano composite flame retardant and the nitrogen-containing carbon forming agent, the nitrogen/phosphorus/silicon synergistic flame retardant effect is achieved, the formed silicon-carbon protective layer can improve the carbon forming rate and has stronger heat insulation and oxygen insulation capabilities, and therefore the flame retardant efficiency is improved.
Detailed Description
The invention is further described with reference to specific embodiments.
Example 1: the flame-retardant smoke-inhibiting PTT polyester composite material comprises the following raw materials in parts by mass: 100 parts of PTT polyester, 80 parts of modified polyester, 25 parts of glass fiber, 10 parts of hydroxide-containing nano composite flame retardant, 20 parts of carbon forming agent, 30 parts of toughening agent, 1 part of coupling agent, 0.5 part of antioxidant and 4 parts of nucleating agent;
wherein the modified polyester is PET, PETG, PCTG, Tritan modified polyester, PEN and PCCD; the toughening agent is maleic anhydride grafted ethylene-propylene-diene copolymer, maleic anhydride grafted styrene-butadiene-styrene copolymer; the nucleating agent is a compound of poly (ethylene-methacrylic acid) sodium salt and sodium stearate in a mass ratio of 1: 1; the coupling agent is a compound of KH550 and KH570 in a mass ratio of 1: 1; the antioxidant is a compound of 1010 and 168 in a mass ratio of 1: 1; the carbon forming agent is ammonium polyphosphate;
the preparation method of the nano composite flame retardant comprises the following steps:
1) placing zirconium phosphate in ethylenediamine, wherein the molar ratio of amine to zirconium nNH3the/nZr is 50: 1; stirring for 48h at normal temperature, centrifuging, washing the precipitate with water and ethanol, drying and dispersing to obtain intercalation-treated zirconium phosphate;
2) pre-drying magnesium hydroxide and aluminum hydroxide at 100 ℃, then placing the magnesium hydroxide and the aluminum hydroxide into a high-speed mixing stirrer, and uniformly stirring the mixture at 100 ℃ to prepare a secondary flame retardant;
3) uniformly mixing the intercalated zirconium phosphate and the auxiliary flame retardant in a mass ratio of 7:3 to prepare a nano composite flame retardant;
a preparation method of a flame-retardant smoke-suppressing PTT polyester composite material comprises the following preparation steps:
s1) mixing the PTT, the modified polyester, the nano-composite flame retardant, the carbon forming agent, the toughening agent, the antioxidant, the nucleating agent and the coupling agent uniformly in a high-speed mixer;
s2) fully mixing the uniformly mixed raw materials with glass fibers through a double-screw extruder, and carrying out melting, extrusion, cooling, granulation and drying to obtain a product; wherein the double-screw extrusion process comprises the following steps: 1-4 region 235 deg.C, 5-10 region 205 deg.C, and 190 deg.C; the screw speed was 300 rpm/min.
Example 2: the flame-retardant smoke-inhibiting PTT polyester composite material comprises the following raw materials in parts by mass: 100 parts of PTT polyester, 40 parts of modified polyester, 50 parts of glass fiber, 20 parts of hydroxide-containing nano composite flame retardant, 5 parts of carbon forming agent, 1 part of toughening agent, 20 parts of coupling agent, 1 part of antioxidant and 0.01 part of nucleating agent;
wherein the modified polyester is PET, PETG, PCTG, Tritan modified polyester, PEN and PCCD; the toughening agent is maleic anhydride grafted ethylene-propylene-diene copolymer, maleic anhydride grafted styrene-butadiene-styrene copolymer; the nucleating agent is a compound of poly (ethylene-methacrylic acid) sodium salt and sodium stearate in a mass ratio of 1.2: 1; the coupling agent is a compound of KH550 and KH570 in a mass ratio of 1.2: 1; the antioxidant is a compound of 1010 and 168 in a mass ratio of 1.2: 1; the carbon forming agent is ammonium polyphosphate; the preparation method of the nano composite flame retardant comprises the following steps:
1) placing zirconium phosphate in ethylenediamine, wherein the molar ratio of amine to zirconium nNH3the/nZr is 40: 1; stirring for 24 hours at normal temperature, centrifuging, washing the precipitate with water and ethanol, drying and dispersing to obtain intercalation-treated zirconium phosphate;
2) pre-drying magnesium hydroxide and aluminum hydroxide at 120 ℃, then placing the magnesium hydroxide and the aluminum hydroxide into a high-speed mixing stirrer, and uniformly stirring the mixture at 120 ℃ to prepare a secondary flame retardant;
3) uniformly mixing the intercalated zirconium phosphate and the auxiliary flame retardant in a mass ratio of 6:4 to prepare a nano composite flame retardant;
a preparation method of a flame-retardant smoke-suppressing PTT polyester composite material comprises the following preparation steps:
s1) mixing the PTT, the modified polyester, the nano-composite flame retardant, the carbon forming agent, the toughening agent, the antioxidant, the nucleating agent and the coupling agent uniformly in a high-speed mixer;
s2) fully mixing the uniformly mixed raw materials with glass fibers through a double-screw extruder, and carrying out melting, extrusion, cooling, granulation and drying to obtain a product; wherein the double-screw extrusion process comprises the following steps: the temperature of the 1-4 area is 240 ℃, the temperature of the 5-10 area is 210 ℃, and the temperature of the machine head is 200 ℃; the screw speed was 350 rpm/min.
Example 3: the flame-retardant smoke-inhibiting PTT polyester composite material comprises the following raw materials in parts by mass: 100 parts of PTT polyester, 5 parts of modified polyester, 5 parts of glass fiber, 30 parts of hydroxide-containing nano composite flame retardant, 30 parts of carbon forming agent, 20 parts of toughening agent, 30 parts of coupling agent, 0.1 part of antioxidant and 2 parts of nucleating agent;
wherein the modified polyester is PET, PETG, PCTG, Tritan modified polyester, PEN and PCCD; the toughening agent is maleic anhydride grafted ethylene-propylene-diene copolymer, maleic anhydride grafted styrene-butadiene-styrene copolymer; the nucleating agent is a compound of poly (ethylene-methacrylic acid) sodium salt and sodium stearate in a mass ratio of 1.1: 1; the coupling agent is a compound of KH550 and KH570 in a mass ratio of 1.1: 1; the antioxidant is a compound of 1010 and 168 in a mass ratio of 1.1: 1; the carbon forming agent is ammonium polyphosphate; the preparation method of the nano composite flame retardant comprises the following steps:
1) placing zirconium phosphate in ethylenediamine, wherein the molar ratio of amine to zirconium nNH3the/nZr is 45: 1; stirring for 35h at normal temperature, centrifuging, washing the precipitate with water and ethanol, drying and dispersing to obtain intercalation-treated zirconium phosphate;
2) pre-drying magnesium hydroxide and aluminum hydroxide at 110 ℃, then placing the magnesium hydroxide and the aluminum hydroxide into a high-speed mixing stirrer, and uniformly stirring the mixture at 110 ℃ to prepare a secondary flame retardant;
3) uniformly mixing the intercalated zirconium phosphate and the auxiliary flame retardant in a mass ratio of 7:4 to prepare a nano composite flame retardant;
a preparation method of a flame-retardant smoke-suppressing PTT polyester composite material comprises the following preparation steps:
s1) mixing the PTT, the modified polyester, the nano-composite flame retardant, the carbon forming agent, the toughening agent, the antioxidant, the nucleating agent and the coupling agent uniformly in a high-speed mixer;
s2) fully mixing the uniformly mixed raw materials with glass fibers through a double-screw extruder, and carrying out melting, extrusion, cooling, granulation and drying to obtain a product; wherein the double-screw extrusion process comprises the following steps: 237 ℃ in a region of 1-4, 208 ℃ in a region of 5-10 and 195 ℃ in a machine head; the screw speed was 320 rpm/min.
Example 4: the difference from the embodiment 1 is that the surface of the nano composite flame retardant is subjected to organic coating treatment, and the method comprises the following coating steps:
a) placing the nano composite flame retardant into deionized water to prepare suspension with the concentration of 15 wt%, then heating to 75 ℃, adding potassium silicate and aqueous solution containing acid or alkali, aging for 1.5h, washing and drying to prepare the amorphous silicon dioxide coated nano composite flame retardant, wherein the thickness of the amorphous silicon dioxide is 1-15 nm; the mass ratio of the amorphous silicon dioxide to the nano composite flame retardant is 10: 100;
b) placing amorphous silicon dioxide coated nano composite flame retardant and resin loaded stannic chloride into ethanol water solution, wherein the mass of a catalyst is 1% of that of the organic coated nano composite flame retardant, then heating to 75 ℃, then dropwise adding 4-vinylbenzyl glycidyl ether, continuously stirring for reaction, returning to normal temperature after the reaction is finished, recovering the catalyst, and carrying out reduced pressure distillation to obtain the organic coated nano composite flame retardant.
Example 5: the difference from the embodiment 1 is that the surface of the nano composite flame retardant is subjected to organic coating treatment, and the method comprises the following coating steps:
a) placing the nano composite flame retardant into deionized water to prepare suspension with the concentration of 10 wt%, then heating to 65 ℃, adding potassium silicate and aqueous solution containing acid or alkali, aging for 1h, washing and drying to prepare the nano composite flame retardant coated by amorphous silicon dioxide, wherein the thickness of the amorphous silicon dioxide is 1-15 nm; the mass ratio of the amorphous silicon dioxide to the nano composite flame retardant is 5: 100;
b) placing amorphous silicon dioxide coated nano composite flame retardant and resin-loaded stannic chloride into ethanol water solution, wherein the mass of a catalyst is 1% of that of the organic coated nano composite flame retardant, then heating to 70 ℃, then dropwise adding 4-vinylbenzyl glycidyl ether, continuously stirring for reaction, returning to normal temperature after the reaction is finished, recovering the catalyst, and carrying out reduced pressure distillation to obtain the organic coated nano composite flame retardant.
Example 6: the difference from the embodiment 1 is that the surface of the nano composite flame retardant is subjected to organic coating treatment, and the method comprises the following coating steps:
a) placing the nano composite flame retardant into deionized water to prepare a suspension with the concentration of 20wt%, then heating to 85 ℃, adding potassium silicate and an aqueous solution containing acid or alkali, aging for 2.5 hours, washing and drying to prepare the amorphous silicon dioxide coated nano composite flame retardant, wherein the thickness of the amorphous silicon dioxide is 1-15 nm; the mass ratio of the amorphous silicon dioxide to the nano composite flame retardant is 20: 100;
b) placing amorphous silicon dioxide coated nano composite flame retardant and resin-loaded tin tetrachloride into an ethanol water solution, heating to 80 ℃, then dropwise adding 4-vinylbenzyl glycidyl ether, continuously stirring for reaction, returning to normal temperature after the reaction is finished, recovering the catalyst, and carrying out reduced pressure distillation to prepare the organic coated nano composite flame retardant.
Comparative example 1: (the difference from the example 1 is that the flame retardant only contains zirconium phosphate and is not subjected to organic coating treatment) the flame-retardant smoke-inhibiting PTT polyester composite material comprises the following raw materials in parts by weight: 100 parts of PTT polyester, 80 parts of modified polyester, 25 parts of glass fiber, 10 parts of flame retardant, 20 parts of carbon forming agent, 30 parts of toughening agent, 1 part of coupling agent, 0.5 part of antioxidant and 4 parts of nucleating agent;
wherein the flame retardant is zirconium phosphate; the modified polyester is PET, PETG, PCTG, Tritan modified polyester, PEN and PCCD; the toughening agent is maleic anhydride grafted ethylene-propylene-diene copolymer, maleic anhydride grafted styrene-butadiene-styrene copolymer; the nucleating agent is a compound of poly (ethylene-methacrylic acid) sodium salt and sodium stearate in a mass ratio of 1: 1; the coupling agent is a compound of KH550 and KH570 in a mass ratio of 1: 1; the antioxidant is a compound of 1010 and 168 in a mass ratio of 1: 1; the carbon forming agent is ammonium polyphosphate;
a preparation method of a flame-retardant smoke-suppressing PTT polyester composite material comprises the following preparation steps:
s1) mixing the PTT, the modified polyester, the nano-composite flame retardant, the carbon forming agent, the toughening agent, the antioxidant, the nucleating agent and the coupling agent uniformly in a high-speed mixer;
s2) fully mixing the uniformly mixed raw materials with glass fibers through a double-screw extruder, and carrying out melting, extrusion, cooling, granulation and drying to obtain a product; wherein the double-screw extrusion process comprises the following steps: 1-4 region 235 deg.C, 5-10 region 205 deg.C, and 190 deg.C; the screw speed was 300 rpm/min.
Comparative example 2: (different from example 4 in that the nanocomposite flame retardant was coated with amorphous silica only and was not grafted with 4-vinylbenzyl glycidyl ether)
The nano composite flame retardant comprises the following coating steps: placing the nano composite flame retardant into deionized water to prepare suspension with the concentration of 15 wt%, then heating to 75 ℃, adding potassium silicate and aqueous solution containing acid or alkali, aging for 1.5h, washing and drying to prepare the amorphous silicon dioxide coated nano composite flame retardant, wherein the thickness of the amorphous silicon dioxide is 1-15 nm; the mass ratio of the amorphous silica to the nano composite flame retardant is 10: 100.
The composite particles prepared in the above examples and comparative examples were dried in vacuum for 4-6 hours at 120-135 deg.C, and then the dried plastic particles were injection molded into samples on an injection molding machine.
The tensile strength test is carried out according to the national standard GB/T1040-92, the size of a test sample is 150 x 10 x 4mm, and the tensile rate is 20 mm/min; the bending performance test is carried out according to the national standard GB// T9341-2000, the size of a test sample is 150 x 10 x 4mm, the bending rate is 40mm/min, and the span is 64 mm; the impact strength of the simply supported beam is carried out according to the national standard GB/T1043-1993, the size of a sample is 80 x 10 x 4mm, and the residual thickness of a gap is 3.2 mm; the thermal deformation temperature is carried out according to national standard GB1634-79, the size of a sample is 120 x 15 x 10mm, and the load is 1.82 Mpa; the material combustion performance test was performed as UL-94 with a sample size of 125 x 13 x 3.2 mm.
The mechanical properties of the material are judged by testing the tensile strength, the bending strength and the impact strength; the heat resistance of the material is judged by testing the heat distortion temperature; the combustion performance of the material is classified into V-0, V-1, V-2 and HB according to UL 94. The smoke density is determined according to the national standard GB/8323-.
From the above data, examples 1-6 and comparative example 2 all have excellent flame retardant and smoke suppression effects, wherein the flame retardant effects of examples 1-3 are increased progressively, because the flame retardant contents of examples 1-3 are increased in sequence, and the flame retardant contents of examples 4-6 are the same as those of example 1, but the flame retardant effect is obviously increased, and the anti-dripping effect is better, because the flame retardants of examples 4-6 are organically coated. Comparative example 1 compared with example 1, the flame retardant agent only contains zirconium phosphate and is not treated by organic coating, so that the flame retardant and smoke suppression effects are poor. In comparative example 2, the flame retardant is only coated by amorphous silica and is not grafted with 4-vinylbenzyl glycidyl ether, so that the flame retardant effect is improved compared with that of example 1 due to the synergistic flame retardant action mechanism of nitrogen/phosphorus/silicon, but the flame retardant effect is not improved due to the fact that 4-vinylbenzyl glycidyl ether is not grafted, and the flame retardant does not have the anti-dripping effect.
Claims (8)
1. The flame-retardant smoke-inhibiting PTT polyester composite material is characterized by comprising the following raw materials in parts by mass: 100 parts of PTT polyester, 5-80 parts of modified polyester, 5-50 parts of glass fiber, 10-30 parts of hydroxide-containing nano composite flame retardant, 5-30 parts of carbon forming agent, 1-30 parts of toughening agent, 1-30 parts of coupling agent, 0.1-1 part of antioxidant and 0.01-4 parts of nucleating agent;
the nano composite flame retardant is obtained by compounding a main flame retardant and an auxiliary flame retardant in a mass ratio of 6-7: 4-3; the main flame retardant is zirconium phosphate, and the auxiliary flame retardant is obtained by compounding magnesium hydroxide and aluminum hydroxide according to the mass ratio of 1-1.2: 1;
the preparation method of the nano composite flame retardant comprises the following steps:
1) placing zirconium phosphate in ethylenediamine, wherein the molar ratio of amine to zirconium nNH3the/nZr is 40-50: 1; stirring for 24-48h at normal temperature, centrifuging, washing the precipitate with water and ethanol, drying and dispersing to obtain intercalation-treated zirconium phosphate;
2) predrying magnesium hydroxide and aluminum hydroxide at the temperature of 100-120 ℃, then placing the magnesium hydroxide and the aluminum hydroxide in a high-speed mixing stirrer, and uniformly stirring the magnesium hydroxide and the aluminum hydroxide at the temperature of 100-120 ℃ to prepare the secondary flame retardant;
3) and uniformly mixing the intercalated zirconium phosphate and the auxiliary flame retardant to prepare the nano composite flame retardant.
2. The flame-retardant smoke-suppressing PTT polyester composite material according to claim 1, wherein the surface of the nano-composite flame retardant is subjected to organic coating treatment, comprising the following coating steps:
a) placing the nano composite flame retardant into deionized water to prepare suspension, then heating to 65-85 ℃, adding a silicon source and an aqueous solution containing acid or alkali, aging for 1-2.5h, washing and drying to prepare the amorphous silicon dioxide coated nano composite flame retardant, wherein the thickness of the amorphous silicon dioxide is 1-15 nm;
b) placing the amorphous silicon dioxide coated nano composite flame retardant and the catalyst in an ethanol water solution, heating to 70-80 ℃, then dropwise adding 4-vinylbenzyl glycidyl ether, continuously stirring for reaction, returning to normal temperature after the reaction is finished, recovering the catalyst, and carrying out reduced pressure distillation to obtain the organic coated nano composite flame retardant.
3. The flame retardant and smoke suppressing PTT polyester composite material according to claim 2, wherein the concentration of the nanocomposite flame retardant in the suspension of step a) is 10-20 wt%.
4. The flame-retardant smoke-suppressing PTT polyester composite material according to claim 2, wherein the mass ratio of the amorphous silica to the nano-composite flame retardant is 5-20: 100.
5. The flame-retardant smoke-suppressing PTT polyester composite material according to claim 2, wherein the catalyst of step b) comprises resin-supported tin tetrachloride, and the mass of the catalyst is 1-2% of that of the organic coated nano composite flame retardant.
6. The flame-retardant smoke-suppressing PTT polyester composite material according to claim 1, wherein the modified polyester comprises one or more of PET, PETG, PCTG, Tritan modified polyester, PEN and PCCD; the toughening agent comprises one or more of maleic anhydride grafted ethylene-propylene-diene copolymer and maleic anhydride grafted styrene-butadiene-styrene copolymer; the nucleating agent comprises a compound of poly (ethylene-methacrylic acid) sodium salt and sodium stearate in a mass ratio of 1-1.2: 1; the coupling agent comprises a compound of KH550 and KH570 in a mass ratio of 1-1.2: 1; the antioxidant comprises a compound of 1010 and 168 in a mass ratio of 1-1.2: 1.
7. The flame retardant smoke suppression PTT polyester composite material according to claim 1, wherein the carbon former comprises a nitrogen-containing carbon former comprising ammonium polyphosphate.
8. A method for preparing the flame-retardant smoke-suppressing PTT polyester composite material as claimed in any one of claims 1 to 7, which is characterized by comprising the following preparation steps:
s1) mixing the PTT, the modified polyester, the nano-composite flame retardant, the carbon forming agent, the toughening agent, the antioxidant, the nucleating agent and the coupling agent uniformly in a high-speed mixer;
s2) fully mixing the uniformly mixed raw materials with glass fibers through a double-screw extruder, and carrying out melting, extrusion, cooling, granulation and drying to obtain a product; wherein the double-screw extrusion process comprises the following steps: the 1-4 area is 235-; the screw rotation speed is 300-350 rpm/min.
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