CN112745641A - Low TVOC flame-retardant reinforced PBT composite material and preparation method and application thereof - Google Patents
Low TVOC flame-retardant reinforced PBT composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a low TVOC flame-retardant reinforced PBT composite material, and a preparation method and application thereof. The low TVOC flame-retardant reinforced PBT composite material comprises the following components in parts by weight: 40-60 parts of PBT resin; 25-40 parts of alkali-free glass fiber; 8-15 parts of a brominated flame retardant; 2-5 parts of a flame-retardant synergist; 0-5 parts of a toughening agent; 0.2-1 part of end-capped hyperbranched polyester; 0.3-1 part of linear low-density polyethylene; 0-1 part of processing aid. According to the invention, the TVOC value of the flame-retardant reinforced PBT composite material is effectively reduced by the sharing of the specifically compatible linear low-density polyethylene LLDPE and the end-capped hyperbranched polyester, so that the flame-retardant reinforced PBT composite material with the flame retardance of 0.8mmV-0 grade of UL-94 standard and the TVOC of less than or equal to 30ppm is obtained, a gas adsorbent is not required to be added, the comprehensive performance of the material is not influenced, and the use requirements in the fields of electronic components in the automotive interior and the electronic and electrical industry can be met.
Description
Technical Field
The invention relates to the technical field of high molecular engineering plastics, and particularly relates to a low TVOC flame-retardant reinforced PBT composite material, and a preparation method and application thereof.
Background
Polybutylene terephthalate (PBT) is an increasingly widely used engineering plastic, has comprehensive and stable mechanical property and better hydrolysis resistance, has lower hygroscopicity than nylon and other materials, and has little influence on the stability of electricity and size. Meanwhile, the PBT has better chemical resistance, solvent resistance and weather resistance, high crystallization speed, good fluidity and excellent forming performance, and also has the advantages of high dielectric strength, low friction coefficient, wear resistance and good bending creep property. The flame-retardant reinforced PBT is one of the most widely industrialized PBT modified products at present, and compared with pure PBT, the introduction of the flame retardant and the glass fiber improves various physical properties and fatigue resistance of the PBT, and reduces the water absorption, creep and molding shrinkage of the material. Due to the advantages, the flame-retardant reinforced PBT is widely applied to the fields of capacitors, relays, automotive upholsteries and the like. However, in the fields of automotive interior and high-demand electronic and electrical products, the TVOC (total volatile organic compound) is highly demanded, and therefore, it is necessary to reduce the TVOC content of the flame-retardant reinforced PBT material.
In the prior art, CN107189371A discloses a low Tvoc flame-retardant PBT composite material and a preparation method thereof, wherein in the disclosed technology, a smell absorbent BX molecular sieve, zinc ricinoleate and the like are mainly used for absorbing and reducing TVOC of a flame-retardant reinforced PBT material.
Disclosure of Invention
The invention aims to solve the technical problems that the existing flame-retardant PBT composite material has a high TVOC value and cannot meet the application requirements, and provides a low TVOC flame-retardant reinforced PBT composite material which is prepared by compounding specific components, particularly by sharing linear low-density polyethylene LLDPE and end-capped hyperbranched polyester.
The invention also aims to provide a preparation method of the low TVOC flame-retardant reinforced PBT composite material.
The invention further aims to provide an application of the low TVOC flame-retardant reinforced PBT composite material in the preparation of electronic components in the automotive interior and the electronic and electrical industry.
The above purpose of the invention is realized by the following technical scheme:
the low TVOC flame-retardant reinforced PBT composite material comprises the following raw materials in parts by weight:
40-60 parts of PBT resin; 25-40 parts of alkali-free glass fiber; 8-15 parts of a brominated flame retardant; 2-5 parts of a flame-retardant synergist; 0-5 parts of a toughening agent; 0.2-1 part of end-capped hyperbranched polyester; 0.3-1 part of linear low-density polyethylene; 0-1 part of processing aid.
The specific functions of the components in the low TVOC flame-retardant reinforced PBT composite material are illustrated as follows:
the alkali-free glass fiber can improve the mechanical strength and the impact resistance of the flame-retardant reinforced PBT composite material;
the brominated flame retardant and the flame-retardant synergist act synergistically to jointly improve the flame-retardant grade of the material;
the toughening agent can improve the toughness and the impact resistance of the material.
Among them, it should be noted that:
the end-capped hyperbranched polyester of the invention is characterized in that: the terminated hydroxyl-terminated hyperbranched polyester or terminated carboxyl-terminated hyperbranched polyester can be, for example, terminated hyperbranched polyester HBP-160 of Wuhan hyperbranched resin technology Inc. or terminated hyperbranched polyester CYD-5300 of Weihaichen molecular new materials Inc.
The low TVOC flame-retardant reinforced PBT composite material realizes the reduction of TVOC mainly by the sharing of linear low-density polyethylene LLDPE and end-capped hyperbranched polyester, and the sharing content of the linear low-density polyethylene LLDPE and the end-capped hyperbranched polyester is also crucial, so that the effect that the TVOC is less than or equal to 30ppm can be realized only by accurately controlling the sharing amount of the linear low-density polyethylene LLDPE and the end-capped hyperbranched polyester within the protection range of the invention.
The TVOC is mainly a resin micromolecular volatile substance separated out from the resin in the long-time baking process, the LLDPE has poor compatibility with the resin, the TVOC is easily separated out to the surface of a material in the processing process, and the shearing of the resin, a screw cylinder and a screw is reduced, so that the generation of resin micromolecules is reduced. The terminated hyperbranched polyester can effectively improve the internal lubrication of the resin in the processing process, reduce the degradation caused by the internal friction of the resin and reduce the generation of small molecular volatile matters. Compared with the end-capped hyperbranched polyester, other hyperbranched polyesters such as carboxyl-terminated hyperbranched polyester can promote internal lubrication and reduce the friction between resin and glass fibers, but volatile substances are easily generated by the hyperbranched polyester, so that the TVOC is reduced disadvantageously, and the hydroxyl-terminated hyperbranched polyester has no obvious effect on promoting the internal lubrication.
The flame retardant and the flame retardant synergist are cooperatively used, so that the prepared low TVOC flame-retardant reinforced PBT composite material has a flame retardant grade of 0.8mmV-0 in UL-94 standard, and TVOC is less than or equal to 30ppm, so that the use requirement in the fields of automotive interiors and electronic components in the electronic and electrical industry can be met.
Furthermore, the low TVOC flame-retardant reinforced PBT composite material provided by the invention has the advantages that the alkali-free glass fiber can improve the tensile strength, the toughening agent can improve the toughness, the low-viscosity resin can improve the melt index, the tensile strength is more than 130MPa, and the impact strength is more than or equal to 10kJ/m2The melt index is more than or equal to 20g/10min (250 ℃/2.16KG), and the high-strength high-fluidity high-strength high-melt-index high.
The low-TVOC flame-retardant reinforced PBT composite material obtained by the invention can effectively reduce the TVOC content of the flame-retardant PBT material without adding a gas adsorbent, has no influence on the comprehensive performance of the material without adding the gas adsorbent, does not undergo any special post-treatment, and has the advantage of easy processing.
Preferably, the feed comprises the following raw materials in parts by weight:
40-60 parts of PBT resin; 25-40 parts of alkali-free glass fiber; 8-15 parts of a brominated flame retardant; 2-5 parts of a flame-retardant synergist; 0-5 parts of a toughening agent; 0.2-1 part of end-capped hyperbranched polyester; 0.3-1 part of linear low-density polyethylene; 0-1 part of processing aid.
Further preferably, the feed comprises the following raw materials in parts by weight:
40-60 parts of PBT resin; 25-40 parts of alkali-free glass fiber; 8-15 parts of a brominated flame retardant; 2-5 parts of a flame-retardant synergist; 0-5 parts of a toughening agent; 0.4 part of end-capped hyperbranched polyester; 0.4 part of linear low-density polyethylene; 0-1 part of processing aid.
Preferably, the linear low density polyethylene is linear low density polyethylene with a melting point of 120-130 ℃. The melting point is too low, the molecular weight is small, the self thermal stability is reduced, volatile matter micromolecules are easy to generate, the melting point is too high, the molecular weight is large, the dispersity is poor, and the volatile matter micromolecules are easy to separate out.
Preferably, the PBT resin is polybutylene terephthalate, and the intrinsic viscosity of the resin is 0.7-1.3 dl/g. The PBT resin with the viscosity range is beneficial to actual injection molding processing, the stability of the injection molding process is not beneficial to the over-low or over-high viscosity, the over-low viscosity and the over-high small molecules are realized, and the TVOC is improved.
Wherein the intrinsic viscosity of the PBT resin is detected by the method GB/T14190-2017.
Preferably, the alkali-free glass fiber is preferably an alkali-free glass fiber treated with a coupling agent. Compared with the common glass fiber, the alkali-free glass fiber has high tensile strength and good electrical insulation, the interface strength and the performance of the glass fiber and resin can be effectively improved after the treatment of the coupling agent, and the coupling agent is mainly a silane coupling agent.
Preferably, the brominated flame retardant is one or more of brominated epoxy, brominated polystyrene, brominated polycarbonate, decabromodiphenylethane or pentabromobenzyl polyacrylate. The flame retardant has the advantages of good thermal stability, high bromine content, no precipitation and the like, and is more beneficial to material processing and forming and flame retardance improvement.
Preferably, the flame retardant synergist is an antimony-containing flame retardant, preferably antimony white or sodium antimonate. The antimony white, the sodium antimonate and the bromine flame retardant have good synergistic flame retardant effect, good thermal stability and small influence on performance.
Preferably, the toughening agent is one or more of ethylene-acrylate-glycidyl methacrylate terpolymer, ethylene-acrylate binary copolymer, ethylene-vinyl acetate and glycidyl methacrylate grafted ethylene-octene copolymer.
Preferably, the processing aid comprises a lubricant and an antioxidant, wherein the lubricant is one or more of aliphatic carboxylic ester, erucamide, ethylene bis stearamide, montmorillonite esters, polyethylene wax and oxidized polyethylene wax; the antioxidant is one or more of hindered phenol antioxidant, phosphite antioxidant, and organic sulfur antioxidant.
The invention also discloses a preparation method of the low TVOC flame-retardant reinforced PBT composite material, which comprises the following steps:
s1, uniformly mixing the dried PBT resin, the brominated flame retardant, the flame-retardant synergist, the alkali-free glass fiber, the toughening agent, the end-capped hyperbranched polyester, the linear low-density polyethylene and the processing aid to obtain a mixed material;
and S2, feeding the mixed material into a double-screw extruder, extruding, bracing, cooling, granulating and drying by the double-screw extruder to obtain the low TVOC flame-retardant reinforced PBT composite material.
Preferably, the feeding material of the double-screw extruder is 450-800 kg/hour; the temperature of each section of screw of the double-screw extruder from the feed inlet to the head is 220-230 ℃, 230-240 ℃, 203-240 ℃, 240-250 ℃, 250-260 ℃, 240-250 ℃, 230-240 ℃ and the screw rotating speed is 250-400 rpm.
The mechanical property of the processing temperature in the range is optimal, the plasticizing is not good for dispersion when the temperature is too low, and the resin decomposition is not good for performance when the temperature is too high.
Meanwhile, the application of the low TVOC flame-retardant reinforced PBT composite material in the preparation of electronic components in the automotive interior and the electronic and electrical industry is also within the protection scope of the invention.
The low TVOC flame-retardant reinforced PBT composite material has a UL-94 standard of 0.8mmV-0 grade, and simultaneously, the TVOC is less than or equal to 30ppm, can meet the use requirements in the fields of automotive trim and electronic components in the electronic and electrical industry, and can be widely applied to the preparation of the electronic components in the automotive trim and the electronic and electrical industry.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a low TVOC flame-retardant reinforced PBT composite material, which effectively reduces the TVOC value of the flame-retardant reinforced PBT composite material through the sharing of the specifically compatible linear low-density polyethylene LLDPE and the end-capping hyperbranched polyester, obtains the flame-retardant reinforced PBT composite material with the flame retardance of 0.8mmV-0 grade of UL-94 standard and the TVOC of less than or equal to 30ppm, does not need to add a gas adsorbent, has no influence on the comprehensive performance of the material, and can meet the use requirements in the fields of electronic components in the automotive interior and the electronic and electrical industry.
Meanwhile, the tensile strength of the low TVOC flame-retardant reinforced PBT composite material is more than 130MPa, and the impact strength is more than or equal to 10kJ/m2The melt index is more than or equal to 20g/10min (250 ℃/2.16KG), and the high-strength high-fluidity high-strength high-melt-index high-strength high-melt-index high-.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Wherein, the raw material sources of the examples and the comparative examples of the invention are as follows:
PBT resin: specific resin designations: PBT 1200-211M, Taiwan Changchun, resin viscosity 0.8 dl/g; PBT GX110, Jiangsu instrumented chemical fiber, resin viscosity 0.67 dl/g;
brominated flame retardants are selected from: brominated epoxy F-2100, Israel ICL; brominated polystyrene SAYTEX 621, american yabao; decabromodiphenylethane SAYTEX 4010, yabao, usa; polyacrylic acid pentabromobenzyl ester FR-1025, Israel ICL; brominated polycarbonate FG8500, imperial japan;
synergistic flame retardant: antimony white S-05N, Chenzhou antimony industry; sodium antimonate SA-F;
a toughening agent: ethylene-acrylate-glycidyl methacrylate terpolymer, designation PTW (dupont); ethylene-methyl acrylate dipolymer, designation ELVALOY AC 1125 (dupont);
alkali-free glass fibers are respectively selected from: ECS13-4.5-534A (glass fiber diameter 13 μm, boulder group); ECS10-4.5-T436H (glass fiber diameter 10 μm, Mount Taishan fiberglass Co., Ltd.);
hyperbranched polyester: carboxyl-terminated hyperbranched resin Hyper C100, terminated hyperbranched polyester HBP-160, Wuhan hyperbranched resin science and technology Limited; hydroxyl-terminated hyperbranched polyester CYD-C600, Waishahi molecular New materials Co., Ltd;
linear low density polyethylene: LLDPE 6101RQ, Exxon Mobil USA, melting point 125 ℃; LLDPE 1018FA, Exxon Mobil, USA, melting point 119 ℃;
processing aid, antioxidant (1010, 168, 412S, Rianlong) and lubricant (PETS, Italy hair base)
Example 1
The low TVOC flame-retardant reinforced PBT composite material comprises the following raw materials in parts by weight:
53.7 parts of PBT resin; 30 parts of alkali-free glass fiber; 10 parts of a brominated flame retardant; 3 parts of a flame-retardant synergist; 2 parts of a toughening agent; 0.2 part of end-capped hyperbranched polyester; 0.3 part of linear low-density polyethylene; and 0.8 part of processing aid.
Wherein the melting point of the linear low-density polyethylene is 125 ℃;
the PBT resin is polybutylene terephthalate, and the intrinsic viscosity of the PBT resin is 0.8dl/g
The alkali-free glass fiber is treated by a coupling agent and has a diameter of 10 mu m;
the brominated flame retardant is brominated epoxy;
the flame-retardant synergist comprises: antimony trioxide;
the toughening agent is: PTW;
the processing aids are: PETs.
The preparation method of the low TVOC flame-retardant reinforced PBT composite material comprises the following steps:
s1, drying the PBT resin at 130 ℃ for more than 3 hours, controlling the water content to be less than 0.03 part, and uniformly mixing the dried PBT resin, the brominated flame retardant, the flame-retardant synergist, the alkali-free glass fiber, the toughening agent, the end-capped hyperbranched polyester, the linear low-density polyethylene and the processing aid to obtain a mixed material;
s2, feeding the mixed material into a double-screw extruder, adjusting the feeding amount to be 450-800 kg/h, feeding the mixed material in the double-screw extruder in a side-feeding mode, adding alkali-free glass fiber in proportion, wherein the temperatures of all sections of screws of the double-screw extruder from a feeding port to a machine head are 230 ℃, 240 ℃, 250 ℃, 260 ℃, 240 ℃, 230 ℃ and 220 ℃, and the rotating speeds of the screws are 400rpm, fully melting, plasticizing, kneading and mixing, extruding through the machine head, bracing, cooling, granulating, drying and finally packaging under the conveying and shearing action of the double-screw extruder to obtain the low TVOC flame-retardant reinforced PBT.
Example 2
The low TVOC flame-retardant reinforced PBT composite material comprises the following raw materials in parts by weight:
52.2 parts of PBT resin; 30 parts of alkali-free glass fiber; 10 parts of a brominated flame retardant; 3 parts of a flame-retardant synergist; 2 parts of a toughening agent; 1 part of end-capped hyperbranched polyester; 1 part of linear low-density polyethylene; and 0.8 part of processing aid.
Wherein the melting point of the linear low-density polyethylene is 125 ℃;
the PBT resin is polybutylene terephthalate, and the intrinsic viscosity of the resin is 0.8dl/g
The alkali-free glass fiber is treated by a coupling agent and has a diameter of 10 mu m;
the brominated flame retardant is brominated epoxy;
the flame-retardant synergist comprises: antimony trioxide;
the toughening agent is: PTW;
the processing aids are: PETs.
The preparation method of the low TVOC flame-retardant reinforced PBT composite material is the same as that of the example 1.
Example 3
The low TVOC flame-retardant reinforced PBT composite material comprises the following raw materials in parts by weight:
53.2 parts of PBT resin; 30 parts of alkali-free glass fiber; 10 parts of a brominated flame retardant; 3 parts of a flame-retardant synergist; 2 parts of a toughening agent; 0.5 part of end-capped hyperbranched polyester; 0.5 part of linear low-density polyethylene; and 0.8 part of processing aid.
Wherein the melting point of the linear low-density polyethylene is 125 ℃;
the PBT resin is polybutylene terephthalate, and the intrinsic viscosity of the resin is 0.8dl/g
The alkali-free glass fiber is treated by a coupling agent and has a diameter of 10 mu m;
the brominated flame retardant is brominated epoxy;
the flame-retardant synergist comprises: antimony trioxide;
the toughening agent is: PTW;
the processing aids are: PETs.
The preparation method of the low TVOC flame-retardant reinforced PBT composite material is the same as that of the example 1.
Example 4
The low TVOC flame-retardant reinforced PBT composite material comprises the following raw materials in parts by weight:
53.4 parts of PBT resin; 30 parts of alkali-free glass fiber; 10 parts of a brominated flame retardant; 3 parts of a flame-retardant synergist; 2 parts of a toughening agent; 0.4 part of end-capped hyperbranched polyester; 0.4 part of linear low-density polyethylene; and 0.8 part of processing aid.
Wherein the melting point of the linear low-density polyethylene is 125 ℃;
the PBT resin is polybutylene terephthalate, and the intrinsic viscosity of the resin is 0.8dl/g
The alkali-free glass fiber is treated by a coupling agent and has a diameter of 10 mu m;
the brominated flame retardant is brominated epoxy;
the flame-retardant synergist comprises: antimony trioxide;
the toughening agent is: PTW;
the processing aids are: PETs.
The preparation method of the low TVOC flame-retardant reinforced PBT composite material is the same as that of the example 1.
Example 5
The low TVOC flame-retardant reinforced PBT composite material comprises the following raw materials in parts by weight:
53.4 parts of PBT resin; 30 parts of alkali-free glass fiber; 10 parts of a brominated flame retardant; 3 parts of a flame-retardant synergist; 2 parts of a toughening agent; 0.4 part of end-capped hyperbranched polyester; 0.4 part of linear low-density polyethylene; and 0.8 part of processing aid.
Wherein the melting point of the linear low-density polyethylene is 125 ℃;
the PBT resin is polybutylene terephthalate, and the intrinsic viscosity of the resin is 0.67dl/g
The alkali-free glass fiber is treated by a coupling agent and has a diameter of 10 mu m;
the brominated flame retardant is brominated epoxy;
the flame-retardant synergist comprises: antimony trioxide;
the toughening agent is: PTW;
the processing aids are: PETs.
The preparation method of the low TVOC flame-retardant reinforced PBT composite material is the same as that of the example 1.
Example 6
The low TVOC flame-retardant reinforced PBT composite material comprises the following raw materials in parts by weight:
53.4 parts of PBT resin; 30 parts of alkali-free glass fiber; 10 parts of a brominated flame retardant; 3 parts of a flame-retardant synergist; 2 parts of a toughening agent; 0.4 part of end-capped hyperbranched polyester; 0.4 part of linear low-density polyethylene; and 0.8 part of processing aid. Wherein the melting point of the linear low density polyethylene is 119 ℃;
the PBT resin is polybutylene terephthalate, and the intrinsic viscosity of the resin is 0.8dl/g
The alkali-free glass fiber is treated by a coupling agent and has a diameter of 10 mu m;
the brominated flame retardant is brominated epoxy;
the flame-retardant synergist comprises: antimony trioxide
The toughening agent is: PTW;
the processing aids are: PETs.
The preparation method of the low TVOC flame-retardant reinforced PBT composite material is the same as that of the example 1.
Comparative example 1
The flame-retardant reinforced PBT composite material comprises the following raw materials in parts by weight:
54.2 parts of PBT resin; 30 parts of alkali-free glass fiber; 10 parts of a brominated flame retardant; 3 parts of a flame-retardant synergist; 2 parts of a toughening agent; and 0.8 part of processing aid.
Wherein the melting point of the linear low-density polyethylene is 125 ℃;
the PBT resin is polybutylene terephthalate, and the intrinsic viscosity of the resin is 0.8dl/g
The alkali-free glass fiber is treated by a coupling agent and has a diameter of 10 mu m;
the brominated flame retardant is brominated epoxy;
the flame-retardant synergist comprises: antimony trioxide
The toughening agent is: PTW;
the processing aids are: PETs.
The preparation method of the flame-retardant reinforced PBT composite material is the same as that of example 1.
Comparative example 2
The low TVOC flame-retardant reinforced PBT composite material comprises the following raw materials in parts by weight:
53.4 parts of PBT resin; 30 parts of alkali-free glass fiber; 10 parts of a brominated flame retardant; 3 parts of a flame-retardant synergist; 2 parts of a toughening agent; 0.8 part of end-capped hyperbranched polyester; and 0.8 part of processing aid.
Wherein the melting point of the linear low-density polyethylene is 125 ℃;
the PBT resin is polybutylene terephthalate, and the intrinsic viscosity of the resin is 0.8dl/g
The alkali-free glass fiber is treated by a coupling agent and has a diameter of 10 mu m;
the brominated flame retardant is brominated epoxy;
the flame-retardant synergist comprises: antimony trioxide
The toughening agent is: PTW;
the processing aids are: PETs.
The preparation method of the flame-retardant reinforced PBT composite material is the same as that of example 1.
Comparative example 3
The low TVOC flame-retardant reinforced PBT composite material comprises the following raw materials in parts by weight:
53.4 parts of PBT resin; 30 parts of alkali-free glass fiber; 10 parts of a brominated flame retardant; 3 parts of a flame-retardant synergist; 2 parts of a toughening agent; 0.8 part of linear low-density polyethylene; and 0.8 part of processing aid.
Wherein the melting point of the linear low-density polyethylene is 125 ℃;
the PBT resin is polybutylene terephthalate, and the intrinsic viscosity of the resin is 0.8 dl/g;
the alkali-free glass fiber is treated by a coupling agent and has a diameter of 10 mu m;
the brominated flame retardant is brominated epoxy;
the flame-retardant synergist comprises: antimony trioxide
The toughening agent is: PTW;
the processing aids are: PETs.
The preparation method of the flame-retardant reinforced PBT composite material is the same as that of example 1.
Comparative example 4
The low TVOC flame-retardant reinforced PBT composite material comprises the following raw materials in parts by weight:
53.4 parts of PBT resin; 30 parts of alkali-free glass fiber; 10 parts of a brominated flame retardant; 3 parts of a flame-retardant synergist; 2 parts of a toughening agent; 0.4 part of carboxyl-terminated hyperbranched polyester; 0.4 part of linear low-density polyethylene; and 0.8 part of processing aid.
Wherein the melting point of the linear low-density polyethylene is 125 ℃;
the PBT resin is polybutylene terephthalate, and the intrinsic viscosity of the resin is 0.8dl/g
The alkali-free glass fiber is treated by a coupling agent and has a diameter of 10 mu m;
the brominated flame retardant is brominated epoxy;
the flame-retardant synergist comprises: antimony trioxide
The toughening agent is: PTW;
the processing aids are: PETs.
The preparation method of the flame-retardant reinforced PBT composite material is the same as that of example 1.
Comparative example 5
The low TVOC flame-retardant reinforced PBT composite material comprises the following raw materials in parts by weight:
53.4 parts of PBT resin; 30 parts of alkali-free glass fiber; 10 parts of a brominated flame retardant; 3 parts of a flame-retardant synergist; 2 parts of a toughening agent; 0.4 part of hydroxyl-terminated hyperbranched polyester; 0.4 part of linear low-density polyethylene; and 0.8 part of processing aid.
Wherein the melting point of the linear low-density polyethylene is 125 ℃;
the PBT resin is polybutylene terephthalate, and the intrinsic viscosity of the resin is 0.8dl/g
The alkali-free glass fiber is treated by a coupling agent and has a diameter of 10 mu m;
the brominated flame retardant is brominated epoxy;
the flame-retardant synergist comprises: antimony trioxide
The toughening agent is: PTW;
the processing aids are: PETs.
The preparation method of the flame-retardant reinforced PBT composite material is the same as that of example 1.
Result detection
1. TVOC test
The specific method of TVOC test is as follows:
(1) weighing 200 +/-0.0001 g of sample of the particles which are extruded and cut into granules and are not dried, and putting the sample into a headspace bottle;
(2) the sealed headspace vials were heated at 120 ℃ for 5h (three for each sample in parallel);
(3) the syringe is inserted into the vial to allow the volatile organics to be transported to the gas chromatograph for analysis.
Drawing a standard curve:
(1) preparing 7 calibration solutions of 0.1g,0.5g,1g,5g,10g,50g and 100g acetone (to the nearest 0.0001g) per liter of n-butanol;
(2) injecting 7 calibration solutions with different concentrations into an empty closed headspace bottle by using a 5-microliter injector at the volume of 2 microliter +/-0.02 microliter (namely the injection error is 1 percent at the maximum) per 10ml glass bottle, and tightly covering the bottle cap;
(3) placing the sample into a headspace instrument, keeping the temperature at 120 ℃ for 1h, performing operation analysis according to general test specifications, and repeatedly testing each calibration solution for 3 times.
(4) Respectively measuring the total peak area, drawing a standard curve by taking the content as an abscissa and the total peak area as an ordinate, wherein the slope of the standard curve represents a calibration coefficient K (G)
The total emission EG of the sample carbon is given by the following formula:
unit: μ g C/g (μ g carbon per g sample)
In the formula: the coefficient 0.6402 represents the carbon content in acetone;
TVOC＝EG×0.04555
unit: ppm;
in the formula: coefficient 0.04555 represents TVOC and EGA conversion factor of (d);
2. other Performance detection
(1) Preparing a test sample wafer according to corresponding standard injection molding;
(2) the tensile strength is tested according to ISO 527-.
The specific detection results are shown in table 1 below:
TABLE 1 test results
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The low TVOC flame-retardant reinforced PBT composite material is characterized by comprising the following components in parts by weight:
40-60 parts of PBT resin; 25-40 parts of alkali-free glass fiber; 8-15 parts of a brominated flame retardant; 2-5 parts of a flame-retardant synergist; 0-5 parts of a toughening agent; 0.2-1 part of end-capped hyperbranched polyester; 0.3-1 part of linear low-density polyethylene; 0-1 part of processing aid.
2. The low TVOC flame retardant reinforced PBT composite material of claim 1, which comprises the following raw materials in parts by weight:
40-60 parts of PBT resin; 25-40 parts of alkali-free glass fiber; 8-15 parts of a brominated flame retardant; 2-5 parts of a flame-retardant synergist; 0-5 parts of a toughening agent; 0.4-0.5 part of end-capped hyperbranched polyester; 0.4-0.5 part of linear low-density polyethylene; 0-1 part of processing aid.
3. The low TVOC flame retardant reinforced PBT composite material of claim 2, which comprises the following raw materials in parts by weight:
40-60 parts of PBT resin; 25-40 parts of alkali-free glass fiber; 8-15 parts of a brominated flame retardant; 2-5 parts of a flame-retardant synergist; 0-5 parts of a toughening agent; 0.4 part of end-capped hyperbranched polyester; 0.4 part of linear low-density polyethylene; 0-1 part of processing aid.
4. The low TVOC flame retardant reinforced PBT composite material of claim 1, wherein the linear low density polyethylene is a linear low density polyethylene having a melting point of 120 to 130 ℃.
5. The low TVOC flame retardant reinforced PBT composite material of claim 1, wherein the PBT resin is polybutylene terephthalate, and the intrinsic viscosity of the PBT resin is 0.7 to 1.3 dl/g.
6. The low TVOC flame retardant reinforced PBT composite of claim 1, wherein the alkali-free glass fibers are preferably alkali-free glass fibers treated with a coupling agent.
7. The low TVOC flame retardant reinforced PBT composite material of claim 1, wherein the brominated flame retardant is one or more of brominated epoxy, brominated polystyrene, brominated polycarbonate, decabromodiphenylethane, or pentabromobenzyl polyacrylate.
8. The preparation method of the low TVOC flame-retardant reinforced PBT composite material is characterized by comprising the following steps of:
s1, uniformly mixing the dried PBT resin, the brominated flame retardant, the flame-retardant synergist, the alkali-free glass fiber, the toughening agent, the end-capped hyperbranched polyester, the linear low-density polyethylene and the processing aid to obtain a mixed material;
and S2, feeding the mixed material into a double-screw extruder, extruding, bracing, cooling, granulating and drying by the double-screw extruder to obtain the low TVOC flame-retardant reinforced PBT composite material.
9. The preparation method according to claim 8, wherein the feeding speed of the twin-screw extruder is 450 to 800 kg/hour; the temperature of each section of screw of the double-screw extruder from the feed inlet to the head is 220-230 ℃, 230-240 ℃, 203-240 ℃, 240-250 ℃, 250-260 ℃, 240-250 ℃, 230-240 ℃ and the screw rotating speed is 250-400 rpm.
10. The application of the low TVOC flame-retardant reinforced PBT composite material as claimed in any one of claims 1 to 7 in the preparation of electronic components for automotive interiors and electronic and electrical industries.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716715A (en) * | 2022-04-06 | 2022-07-08 | 江阴市宏丰塑业有限公司 | Light wear-resistant PBT (polybutylene terephthalate) composite material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110152457A1 (en) * | 2009-12-17 | 2011-06-23 | E. I. Du Pont De Nemours And Company | Polyester Compositions with Good Melt Rheological Properties |
| US20110147998A1 (en) * | 2009-12-17 | 2011-06-23 | E.I. Du Pont De Nemours And Company | Polyester Compositions with Good Melt Rheological Properties |
| CN107189371A (en) * | 2017-06-26 | 2017-09-22 | 东莞市东翔塑胶有限公司 | A kind of low Tvoc anti-flaming PBT composites and preparation method thereof |
| CN107266880A (en) * | 2017-07-24 | 2017-10-20 | 武汉顺威赛特工程塑料有限公司 | A kind of high flow enhuancement flame-retardant PBT material and preparation method thereof |
| CN109651777A (en) * | 2018-12-27 | 2019-04-19 | 华润化学材料科技有限公司 | The dedicated impregnant of thermoplastic composite polyester |
| CN110204835A (en) * | 2019-05-24 | 2019-09-06 | 武汉金发科技有限公司 | A kind of toughening agent composition and a kind of thermoplas tic resin composite and preparation method thereof |
-
2020
- 2020-12-15 CN CN202011477113.2A patent/CN112745641B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110152457A1 (en) * | 2009-12-17 | 2011-06-23 | E. I. Du Pont De Nemours And Company | Polyester Compositions with Good Melt Rheological Properties |
| US20110147998A1 (en) * | 2009-12-17 | 2011-06-23 | E.I. Du Pont De Nemours And Company | Polyester Compositions with Good Melt Rheological Properties |
| CN107189371A (en) * | 2017-06-26 | 2017-09-22 | 东莞市东翔塑胶有限公司 | A kind of low Tvoc anti-flaming PBT composites and preparation method thereof |
| CN107266880A (en) * | 2017-07-24 | 2017-10-20 | 武汉顺威赛特工程塑料有限公司 | A kind of high flow enhuancement flame-retardant PBT material and preparation method thereof |
| CN109651777A (en) * | 2018-12-27 | 2019-04-19 | 华润化学材料科技有限公司 | The dedicated impregnant of thermoplastic composite polyester |
| CN110204835A (en) * | 2019-05-24 | 2019-09-06 | 武汉金发科技有限公司 | A kind of toughening agent composition and a kind of thermoplas tic resin composite and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716715A (en) * | 2022-04-06 | 2022-07-08 | 江阴市宏丰塑业有限公司 | Light wear-resistant PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN114716715B (en) * | 2022-04-06 | 2023-09-22 | 江苏普非尔塑料科技有限公司 | Light wear-resistant PBT composite material and preparation method thereof |
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Denomination of invention: A low TVOC flame retardant reinforced PBT composite material and its preparation method and application Effective date of registration: 20230927 Granted publication date: 20220419 Pledgee: Guangzhou Baiyun sub branch of Agricultural Bank of China Ltd. Pledgor: KINGFA SCI. & TECH. Co.,Ltd. Registration number: Y2023980059571 |