CN104672811A - Environment-friendly flame-retardant antistatic reinforced PBT/PET (polybutylene terephthalate/polyethylene terephthalate) composite material - Google Patents

Abstract

The invention discloses an environment-friendly flame-retardant antistatic reinforced PBT/PET (polybutylene terephthalate/polyethylene terephthalate) composite material which is composed of the following components in percentage by mass: 20-50% of PBT resin, 20-50% of PET resin, 5-15% of compound halogen-free flame retardant, 1-3% of antistatic agent, 5-15% of reinforcer, 2-6% of compatilizer, 1-3% of stabilizing agent, 0.5-1% of nucleating agent, 0.1-1% of antioxidant and 0.1-1% of coupling agent. Compared with the prior art, the blend-modified environment-friendly flame-retardant antistatic reinforced PBT/PET composite material has the advantages of high heat-deformation temperature, low shrinkage, high strength, favorable rigidity, creep and fatigue resistance, favorable mechanical properties, favorable electric properties, obvious and durable antistatic effect, high flame-retardant efficiency, no halogen, no toxicity, low smoke, environment friendliness and the like, can satisfy the requirements for flame-retardancy grade UL-94 V-0, thus, has excellent application prospects, and can be widely used in the fields of home appliances, electronic and electric appliances, automobiles, chemical industry and the like.

Description

Environment-protection flame-proof electrostatic resistance strengthens PBT/PET matrix material

Technical field

The present invention relates to technical field of polymer materials, specifically a kind of environment-protection flame-proof electrostatic resistance strengthens PBT/PET matrix material.

Background technology

PBT/PET(polybutylene terephthalate/polyethylene terephthalate) be the ideal engineering plastics of a kind of over-all properties, it has the features such as the good and good elasticity of high temperature resistant, moisture-proof, resistance to chemical attack, electrical insulation capability, and can good mechanical property be kept in wide temperature range, having a wide range of applications in national economy and new high-tech industry, is a kind of indispensable advanced composite material.But notched Izod impact strength is low, shrinking percentage is large, heat-drawn wire is low, static resistance is not enough, flame retardant resistance is bad shortcoming that unmodified PBT/PET material exists, significantly limit its application.Modification is carried out to PBT/PET and can widen its range of application further.

Summary of the invention

A kind of environment-protection flame-proof electrostatic resistance is the object of the present invention is to provide to strengthen PBT/PET matrix material.

The technical solution adopted for the present invention to solve the technical problems is: environment-protection flame-proof electrostatic resistance strengthens PBT/PET matrix material, and its component by mass percent proportioning is: PBT resin 20% ~ 50%, PET resin 20% ~ 50%, Compositional type halogen-free flame retardants 5% ~ 15%, static inhibitor 1% ~ 3%, toughener 5% ~ 15%, compatilizer 2% ~ 6%, stablizer 1% ~ 3%, nucleator 0.5% ~ 1%, oxidation inhibitor 0.1% ~ 1%, coupling agent 0.1% ~ 1%.

Described PBT resin is polybutylene terephthalate.

Described PET resin is polyethylene terephthalate.

Described Compositional type halogen-free flame retardants is the compound of dihydroxyphenyl propane two diphenyl phosphoester (BDP) 40wt%, polydimethylsiloxane (PDMS) 40wt% and magnesium hydroxide 20wt% three mixing, and wherein magnesium hydroxide surface is through silane coupler modified process and modified particle diameter is less than 2 μm.

Described static inhibitor is commercially available HDC-102 static inhibitor or HBS-510 static inhibitor.

Described toughener is the one in nano-calcium carbonate, gas phase nano silicon-dioxide, nano kaoline.

Described compatilizer is methyl methacrylate-methyl propenoic acid glycidyl-ethylpropylene ter-polymers (MGE).

Described stablizer is carbodiimide.

Described nucleator is ethylene-methyl methacrylate sodium ion polymkeric substance.

Described oxidation inhibitor is the one in antioxidant 1010, antioxidant 1076, antioxidant 1076 and irgasfos 168 compound.

Described coupling agent is aluminium titanium composite coupler.

Above-mentioned environment-protection flame-proof electrostatic resistance strengthens the preparation method of PBT/PET matrix material, comprises the following steps:

(1), by PBT resin at 130 DEG C ~ 140 DEG C dry 3 ~ 5 hours, PET resin at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, toughener at 80 DEG C ~ 85 DEG C dry 30 ~ 45 minutes, stand-by;

(2) the two diphenyl phosphoester (BDP) of dihydroxyphenyl propane, polydimethylsiloxane (PDMS) and the surface magnesium hydroxide that particle diameter is less than 2 μm after silane coupler modified process, is taken by weight ratio, add after mixing in high-speed mixer, discharging obtains Compositional type halogen-free flame retardants, stand-by;

(3), dry toughener and coupling agent is taken by weight ratio, add sonic oscillation producer or rotating speed is not less than in the high-speed mixer of 3000 revs/min, stir 10 ~ 60 minutes at 100 DEG C ~ 120 DEG C temperature, obtain the toughener of surface modification, then be cooled to lower than 40 DEG C of dischargings, stand-by;

(4), dry PBT resin and PET resin is taken by weight ratio, add in high-speed mixer, mix 3 ~ 5 minutes, add the toughener that step (3) obtains surface modification again, add the Compositional type halogen-free flame retardants, static inhibitor, compatilizer, stablizer, nucleator, the oxidation inhibitor that take by weight ratio simultaneously, continue mixing 5 ~ 30 minutes, make fully to mix rear discharging;

(5), add in twin screw extruder by the compound of step (4), at 230 DEG C ~ 260 DEG C, through plastifying, mixing is extruded, cooling granulation, gets product.

The invention has the beneficial effects as follows, compared with prior art, the present invention strengthens PBT/PET matrix material by the environment-protection flame-proof electrostatic resistance that blending and modifying is obtained, have that heat-drawn wire is high, shrinking percentage is low, intensity is high, good rigidly, resistance to creep and antifatigue, good mechanical property, excellent electrical properties, and antistatic effect significantly, lastingly, flame-retarded efficiency is high and reach the requirement of Halogen, nontoxic, low cigarette, environmental protection and UL-94 V-0 flame retardant rating, thus there is fabulous application prospect, the fields such as household electrical appliances, electronic apparatus, automobile, chemical industry can be widely used in.

Embodiment

Technical scheme of the present invention is further illustrated below in conjunction with specific embodiment.

Embodiment 1:

A kind of environment-protection flame-proof electrostatic resistance strengthens PBT/PET matrix material, and its component by mass percent proportioning is: PBT resin 35%, PET resin 35%, Compositional type halogen-free flame retardants 10%, HDC-102 static inhibitor 2%, nano-calcium carbonate 10%, methyl methacrylate-methyl propenoic acid glycidyl-ethylpropylene ter-polymers (MGE) 4%, carbodiimide 2%, ethylene-methyl methacrylate sodium ion polymkeric substance 1%, antioxidant 1010 0.8%, aluminium titanium composite coupler 0.2%.Wherein, described Compositional type halogen-free flame retardants is the compound of dihydroxyphenyl propane two diphenyl phosphoester (BDP) 40wt%, polydimethylsiloxane (PDMS) 40wt% and magnesium hydroxide 20wt% three mixing, and wherein magnesium hydroxide surface is through silane coupler modified process and modified particle diameter is less than 2 μm.

Preparation method: (1), by PBT resin at 130 DEG C ~ 140 DEG C dry 3 ~ 5 hours, PET resin at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, nano-calcium carbonate at 80 DEG C ~ 85 DEG C dry 30 ~ 45 minutes, stand-by; (2) the two diphenyl phosphoester (BDP) of dihydroxyphenyl propane, polydimethylsiloxane (PDMS) and the surface magnesium hydroxide that particle diameter is less than 2 μm after silane coupler modified process, is taken by weight ratio, add after mixing in high-speed mixer, discharging obtains Compositional type halogen-free flame retardants, stand-by; (3), dry nano-calcium carbonate and aluminium titanium composite coupler is taken by weight ratio, add sonic oscillation producer or rotating speed is not less than in the high-speed mixer of 3000 revs/min, stir 10 ~ 60 minutes at 100 DEG C ~ 120 DEG C temperature, obtain the nano-calcium carbonate of surface modification, then be cooled to lower than 40 DEG C of dischargings, stand-by; (4), dry PBT resin and PET resin is taken by weight ratio, add in high-speed mixer, mix 3 ~ 5 minutes, add the nano-calcium carbonate that step (3) obtains surface modification again, add the Compositional type halogen-free flame retardants, HDC-102 static inhibitor, methyl methacrylate-methyl propenoic acid glycidyl-ethylpropylene ter-polymers (MGE), carbodiimide, ethylene-methyl methacrylate sodium ion polymkeric substance, the antioxidant 1010 that take by weight ratio simultaneously, continue mixing 5 ~ 30 minutes, make fully to mix rear discharging; (5), add in twin screw extruder by the compound of step (4), at 230 DEG C ~ 260 DEG C, through plastifying, mixing is extruded, cooling granulation, gets product.

Embodiment 2:

A kind of environment-protection flame-proof electrostatic resistance strengthens PBT/PET matrix material, and its component by mass percent proportioning is: PBT resin 40%, PET resin 25%, Compositional type halogen-free flame retardants 15%, HBS-510 static inhibitor 3%, gas phase nano silica 1 0%, methyl methacrylate-methyl propenoic acid glycidyl-ethylpropylene ter-polymers (MGE) 4%, carbodiimide 1%, ethylene-methyl methacrylate sodium ion polymkeric substance 0.6%, antioxidant 1076 and irgasfos 168 compound 1%, aluminium titanium composite coupler 0.4%.Wherein, described Compositional type halogen-free flame retardants is the compound of dihydroxyphenyl propane two diphenyl phosphoester (BDP) 40wt%, polydimethylsiloxane (PDMS) 40wt% and magnesium hydroxide 20wt% three mixing, and wherein magnesium hydroxide surface is through silane coupler modified process and modified particle diameter is less than 2 μm.

Preparation method: (1), by PBT resin at 130 DEG C ~ 140 DEG C dry 3 ~ 5 hours, PET resin at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, gas phase nano silicon-dioxide at 80 DEG C ~ 85 DEG C dry 30 ~ 45 minutes, stand-by, (2) the two diphenyl phosphoester (BDP) of dihydroxyphenyl propane, polydimethylsiloxane (PDMS) and the surface magnesium hydroxide that particle diameter is less than 2 μm after silane coupler modified process, is taken by weight ratio, add after mixing in high-speed mixer, discharging obtains Compositional type halogen-free flame retardants, stand-by, (3), dry gas phase nano silicon-dioxide and aluminium titanium composite coupler is taken by weight ratio, add sonic oscillation producer or rotating speed is not less than in the high-speed mixer of 3000 revs/min, stir 10 ~ 60 minutes at 100 DEG C ~ 120 DEG C temperature, obtain the gas phase nano silicon-dioxide of surface modification, then be cooled to lower than 40 DEG C of dischargings, stand-by, (4), take dry PBT resin and PET resin by weight ratio, add in high-speed mixer, mix 3 ~ 5 minutes, add the gas phase nano silicon-dioxide that step (3) obtains surface modification again, add the Compositional type halogen-free flame retardants taken by weight ratio simultaneously, HBS-510 static inhibitor, methyl methacrylate-methyl propenoic acid glycidyl-ethylpropylene ter-polymers (MGE), carbodiimide, ethylene-methyl methacrylate sodium ion polymkeric substance, antioxidant 1076 and irgasfos 168 compound, continue mixing 5 ~ 30 minutes, make fully to mix rear discharging, (5), add in twin screw extruder by the compound of step (4), at 230 DEG C ~ 260 DEG C, through plastifying, mixing is extruded, cooling granulation, gets product.

Claims (10)

1. an environment-protection flame-proof electrostatic resistance strengthens PBT/PET matrix material, it is characterized in that, its component by mass percent proportioning is: PBT resin 20% ~ 50%, PET resin 20% ~ 50%, Compositional type halogen-free flame retardants 5% ~ 15%, static inhibitor 1% ~ 3%, toughener 5% ~ 15%, compatilizer 2% ~ 6%, stablizer 1% ~ 3%, nucleator 0.5% ~ 1%, oxidation inhibitor 0.1% ~ 1%, coupling agent 0.1% ~ 1%.

2. environment-protection flame-proof electrostatic resistance according to claim 1 strengthens PBT/PET matrix material, it is characterized in that, described Compositional type halogen-free flame retardants is the compound of dihydroxyphenyl propane two diphenyl phosphoester (BDP) 40wt%, polydimethylsiloxane (PDMS) 40wt% and magnesium hydroxide 20wt% three mixing, and wherein magnesium hydroxide surface is through silane coupler modified process and modified particle diameter is less than 2 μm.

3. environment-protection flame-proof electrostatic resistance according to claim 1 strengthens PBT/PET matrix material, and it is characterized in that, described static inhibitor is commercially available HDC-102 static inhibitor or HBS-510 static inhibitor.

4. environment-protection flame-proof electrostatic resistance according to claim 1 strengthens PBT/PET matrix material, and it is characterized in that, described toughener is the one in nano-calcium carbonate, gas phase nano silicon-dioxide, nano kaoline.

5. environment-protection flame-proof electrostatic resistance according to claim 1 strengthens PBT/PET matrix material, and it is characterized in that, described compatilizer is methyl methacrylate-methyl propenoic acid glycidyl-ethylpropylene ter-polymers (MGE).

6. environment-protection flame-proof electrostatic resistance according to claim 1 strengthens PBT/PET matrix material, and it is characterized in that, described stablizer is carbodiimide.

7. environment-protection flame-proof electrostatic resistance according to claim 1 strengthens PBT/PET matrix material, and it is characterized in that, described nucleator is ethylene-methyl methacrylate sodium ion polymkeric substance.

8. environment-protection flame-proof electrostatic resistance according to claim 1 strengthens PBT/PET matrix material, and it is characterized in that, described oxidation inhibitor is the one in antioxidant 1010, antioxidant 1076, antioxidant 1076 and irgasfos 168 compound.

9. environment-protection flame-proof electrostatic resistance according to claim 1 strengthens PBT/PET matrix material, and it is characterized in that, described coupling agent is aluminium titanium composite coupler.

10. environment-protection flame-proof electrostatic resistance according to claim 1 strengthens the preparation method of PBT/PET matrix material, it is characterized in that, comprises the following steps:

(1), by PBT resin at 130 DEG C ~ 140 DEG C dry 3 ~ 5 hours, PET resin at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, toughener at 80 DEG C ~ 85 DEG C dry 30 ~ 45 minutes, stand-by;

(2) the two diphenyl phosphoester (BDP) of dihydroxyphenyl propane, polydimethylsiloxane (PDMS) and the surface magnesium hydroxide that particle diameter is less than 2 μm after silane coupler modified process, is taken by weight ratio, add after mixing in high-speed mixer, discharging obtains Compositional type halogen-free flame retardants, stand-by;

(3), dry toughener and coupling agent is taken by weight ratio, add sonic oscillation producer or rotating speed is not less than in the high-speed mixer of 3000 revs/min, stir 10 ~ 60 minutes at 100 DEG C ~ 120 DEG C temperature, obtain the toughener of surface modification, then be cooled to lower than 40 DEG C of dischargings, stand-by;

(4), dry PBT resin and PET resin is taken by weight ratio, add in high-speed mixer, mix 3 ~ 5 minutes, add the toughener that step (3) obtains surface modification again, add the Compositional type halogen-free flame retardants, static inhibitor, compatilizer, stablizer, nucleator, the oxidation inhibitor that take by weight ratio simultaneously, continue mixing 5 ~ 30 minutes, make fully to mix rear discharging;

(5), add in twin screw extruder by the compound of step (4), at 230 DEG C ~ 260 DEG C, through plastifying, mixing is extruded, cooling granulation, gets product.