CN104672809A - Toughened reinforced environment-friendly flame-retardant PBT/PET (polybutylene terephthalate/polyethylene terephthalate) alloy - Google Patents

Abstract

The invention discloses a toughened reinforced environment-friendly flame-retardant PBT/PET (polybutylene terephthalate/polyethylene terephthalate) alloy which is composed of the following components in percentage by mass: 20-60% of PBT, 10-40% of PET, 10-25% of glass fiber, 5-15% of halogen-free flame retardant, 5-15% of nano calcium carbonate, 5-10% of elastomer, 0.5-2% of maleic anhydride, 0.1-1% of diethyl azodiformate, 1-5% of plasticizer, 0.1-1% of composite nucleating agent, 0.1-1% of composite antioxidant and 0.1-2% of lubricant. Compared with the prior art, the nano calcium carbonate subjected to surface modification pretreatment and the elastomer interact and generate grafting reaction to form the core-shell particles using the nano calcium carbonate as the core and the elastomer as the shell, and the core-shell particles are used for performing toughening modification on the PBT/PET alloy, thereby greatly enhancing the notch impact strength, rigidity, heat resistance and corrosion resistance of the alloy system and keeping excellent mechanical, chemical and electric properties; the toughened reinforced environment-friendly flame-retardant PBT/PET alloy has the advantages of favorable flowability, high gloss, no halogen, flame retardancy, high safety, low smoke, no toxicity, high efficiency and low cost, achieves the flame retardancy grade UL94V-0, and can be widely used in the fields of home appliances, electronic and electric appliances, automobile industry, mechanical equipment, textiles and the like.

Description

Toughen and intensify environment-friendly flame retardant PBT and PET alloy

Technical field

The present invention relates to technical field of polymer materials, specifically a kind of toughen and intensify environment-friendly flame retardant PBT and PET alloy.

Background technology

Polybutylene terephthalate (PBT) and polyethylene terephthalate (PET) are the thermoplastic polyesters that 20 century 70s grow up, there is 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 type material.PBT resin crystallization velocity is fast, and second-order transition temperature Tg is low, easily causes uneven in temperature, causes distortion; And PET resin second-order transition temperature is higher, crystallization velocity is slow, and shaping cycle is long.This make PBT and PET resin especially the application of PET resin on engineering plastics be subject to certain restrictions.Utilize copolymerization, blended method, comprehensive PBT, PET performance separately of energy, learns from other's strong points to offset one's weaknesses, makes up the defect in one-component performance, obtain the blend that over-all properties is ideal.Meanwhile, owing to producing the price almost cheap half of PET ethylene glycol used than production PBT butyleneglycol used, with PET resin Substitute For Partial PBT resin, there is very high cost performance.But PBT and PET alloy use as engineering plastics, there is the shortcomings such as notch sensitivity is strong, notched Izod impact strength is low, heat-drawn wire is low, shrinking percentage is large, flame retardant resistance is bad, significantly limit its application.

Summary of the invention

The object of the present invention is to provide a kind of toughen and intensify environment-friendly flame retardant PBT and PET alloy.

The technical solution adopted for the present invention to solve the technical problems is: toughen and intensify environment-friendly flame retardant PBT and PET alloy, and its component by mass percent proportioning is: PBT 20% ~ 60%, PET 10% ~ 40%, glass fibre 10% ~ 25%, halogen-free flame retardants 5% ~ 15%, nano-calcium carbonate 5% ~ 15%, elastomerics 5% ~ 10%, maleic anhydride 0.5% ~ 2%, diethyl azodiformate 0.1% ~ 1%, softening agent 1% ~ 5%, composite nucleating agent 0.1% ~ 1%, composite antioxidant 0.1% ~ 1%, lubricant 0.1% ~ 2%.

Described PBT is polybutylene terephthalate.

Described PET is polyethylene terephthalate.

Described glass fibre is the alkali free glass fibre of surface through silane coupling agent process.

Described halogen-free flame retardants is that organophosphorous fire retardant comprises phosphate flame retardant, phosphorous acid ester fire retardant, phosphonate fire retardant, organophosphorated salt fire retardant, silicone flame retardant comprises polysilane fire retardant, polysiloxane fire retardant, poly organic silicon silsesquioxane fire retardant, and nitrogenated flame retardant comprises one or more the mixture above-mentioned of melamine flame retardants, melamine cyanurate fire retardant.

Described elastomerics is ethylene-octene copolymer (POE).

Described softening agent is polyoxyethylene glycol (PEG).

Described composite nucleating agent is the compound of Sodium Benzoate and ethylene-methyl methacrylate sodium ion polymkeric substance.

Described composite antioxidant is the compound of hindered phenol antioxygen 1076 and phosphite ester kind antioxidant 168.

Described lubricant is TAS-2A or ethylene bis stearic amide (EBS).

Above-mentioned toughen and intensify environment-friendly flame retardant PBT and the preparation method of PET alloy, comprise the following steps:

(1), by PBT at 130 DEG C ~ 140 DEG C dry 3 ~ 5 hours, PET at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, halogen-free flame retardants at 60 DEG C ~ 80 DEG C dry 30 ~ 45 minutes, nano-calcium carbonate at 60 DEG C ~ 80 DEG C dry 30 ~ 45 minutes, stand-by;

(2), taking dry nano-calcium carbonate by weight ratio, to add barrel temperature be in 30 DEG C ~ 80 DEG C high-speed mixers, stir 3 ~ 15 minutes, then the maleic anhydride and diethyl azodiformate that take by weight ratio is added, stir 10 ~ 30 minutes, obtain pretreated nano-calcium carbonate, discharging; Again on 50 DEG C ~ 80 DEG C opening rubber mixing machines by pretreated nano-calcium carbonate and the direct mixed milling of elastomerics that claims by weight ratio even, slice, cooling is broken, the core-shell particles that to obtain take nano-calcium carbonate as core, elastomerics is shell, stand-by;

(3), dry PBT, PET and halogen-free flame retardants is taken by weight ratio, add in high-speed mixer and mix 2 ~ 5 minutes, add the core-shell particles that step (2) obtains again, add the softening agent, composite nucleating agent, composite antioxidant and the lubricant that take by weight ratio simultaneously, continue mixing 5 ~ 30 minutes, make fully to mix rear discharging;

(4), the compound of step (3) is added the main spout of twin screw extruder, the glass fibre taken by weight ratio is added the side spout of twin screw extruder, controlled working temperature is at 210 DEG C ~ 260 DEG C, screw speed 200 ~ 500rpm, through twin screw extruder plasticizing mixing after extrude, cooling granulation, get product.

The invention has the beneficial effects as follows, compared with prior art, the present invention adopts the interphase interaction of the pretreated nano-calcium carbonate of surface modification and elastomerics and graft reaction occurs, being formed with nano-calcium carbonate is core, elastomerics is that the core-shell particles of shell carries out toughening modifying to PBT and PET alloy, the notched Izod impact strength of alloy system can be improved widely, rigidity, thermotolerance and corrosion resistance nature, keep excellent machinery, chemistry and electric property, and there is good mobility and high-luster, halogen-free flameproof safety, low cigarette, nontoxic, efficient and reach UL94 V-0 grade flame retardant effect, and cost is low, household electrical appliances can be widely used in, electronic apparatus, automotive industry, mechanical means, the fields such as weaving.

Embodiment

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

Embodiment 1:

A kind of toughen and intensify environment-friendly flame retardant PBT and PET alloy, its component by mass percent proportioning is: PBT 33%, PET 20%, surface are through compound 0.5%, the TAS-2A 1.5% of the compound 0.8% of the alkali free glass fibre 15% of silane coupling agent process, phosphate flame retardant 10%, nano-calcium carbonate 10%, ethylene-octene copolymer (POE) 5%, maleic anhydride 1%, diethyl azodiformate 0.2%, polyoxyethylene glycol (PEG) 3%, Sodium Benzoate and ethylene-methyl methacrylate sodium ion polymkeric substance, hindered phenol antioxygen 1076 and phosphite ester kind antioxidant 168.

Preparation method: (1), by PBT at 130 DEG C ~ 140 DEG C dry 3 ~ 5 hours, PET at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, phosphate flame retardant at 60 DEG C ~ 80 DEG C dry 30 ~ 45 minutes, nano-calcium carbonate at 60 DEG C ~ 80 DEG C dry 30 ~ 45 minutes, stand-by; (2), taking dry nano-calcium carbonate by weight ratio, to add barrel temperature be in 30 DEG C ~ 80 DEG C high-speed mixers, stir 3 ~ 15 minutes, then the maleic anhydride and diethyl azodiformate that take by weight ratio is added, stir 10 ~ 30 minutes, obtain pretreated nano-calcium carbonate, discharging; On 50 DEG C ~ 80 DEG C opening rubber mixing machines, by pretreated nano-calcium carbonate and the ethylene-octene copolymer (POE) that claims by weight ratio, directly mixed milling is even again, slice, cooling is broken, the core-shell particles that to obtain take nano-calcium carbonate as core, ethylene-octene copolymer (POE) is shell, stand-by; (3), dry PBT, PET and phosphate flame retardant is taken by weight ratio, add in high-speed mixer and mix 2 ~ 5 minutes, add the core-shell particles that step (2) obtains again, add compound and the TAS-2A of the compound of polyoxyethylene glycol (PEG), Sodium Benzoate and the ethylene-methyl methacrylate sodium ion polymkeric substance taken by weight ratio, hindered phenol antioxygen 1076 and phosphite ester kind antioxidant 168 simultaneously, continue mixing 5 ~ 30 minutes, make fully to mix rear discharging; (4), the compound of step (3) is added the main spout of twin screw extruder, the surface taken by weight ratio is added the side spout of twin screw extruder through the alkali free glass fibre of silane coupling agent process, controlled working temperature is at 210 DEG C ~ 260 DEG C, screw speed 200 ~ 500rpm, through twin screw extruder plasticizing mixing after extrude, cooling granulation, get product.

Embodiment 2:

A kind of toughen and intensify environment-friendly flame retardant PBT and PET alloy, its component by mass percent proportioning is: PBT 30%, PET 25%, surface is through the alkali free glass fibre 10% of silane coupling agent process, the mixture 15% of phosphonate fire retardant and polysilane fire retardant, nano-calcium carbonate 10%, ethylene-octene copolymer (POE) 5%, maleic anhydride 1%, diethyl azodiformate 0.2%, polyoxyethylene glycol (PEG) 1.5%, the compound 0.5% of Sodium Benzoate and ethylene-methyl methacrylate sodium ion polymkeric substance, the compound 0.8% of hindered phenol antioxygen 1076 and phosphite ester kind antioxidant 168, ethylene bis stearic amide (EBS) 1%.

Preparation method: (1), by PBT at 130 DEG C ~ 140 DEG C dry 3 ~ 5 hours, PET at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, the mixture of phosphonate fire retardant and polysilane fire retardant at 60 DEG C ~ 80 DEG C dry 30 ~ 45 minutes, nano-calcium carbonate at 60 DEG C ~ 80 DEG C dry 30 ~ 45 minutes, stand-by; (2), taking dry nano-calcium carbonate by weight ratio, to add barrel temperature be in 30 DEG C ~ 80 DEG C high-speed mixers, stir 3 ~ 15 minutes, then the maleic anhydride and diethyl azodiformate that take by weight ratio is added, stir 10 ~ 30 minutes, obtain pretreated nano-calcium carbonate, discharging; On 50 DEG C ~ 80 DEG C opening rubber mixing machines, by pretreated nano-calcium carbonate and the ethylene-octene copolymer (POE) that claims by weight ratio, directly mixed milling is even again, slice, cooling is broken, the core-shell particles that to obtain take nano-calcium carbonate as core, ethylene-octene copolymer (POE) is shell, stand-by; (3) dry PBT, PET and the mixture of phosphonate fire retardant and polysilane fire retardant, is taken by weight ratio, add in high-speed mixer and mix 2 ~ 5 minutes, add the core-shell particles that step (2) obtains again, add compound and the ethylene bis stearic amide (EBS) of the compound of polyoxyethylene glycol (PEG), Sodium Benzoate and the ethylene-methyl methacrylate sodium ion polymkeric substance taken by weight ratio, hindered phenol antioxygen 1076 and phosphite ester kind antioxidant 168 simultaneously, continue mixing 5 ~ 30 minutes, make fully to mix rear discharging; (4), the compound of step (3) is added the main spout of twin screw extruder, the surface taken by weight ratio is added the side spout of twin screw extruder through the alkali free glass fibre of silane coupling agent process, controlled working temperature is at 210 DEG C ~ 260 DEG C, screw speed 200 ~ 500rpm, through twin screw extruder plasticizing mixing after extrude, cooling granulation, get product.

Claims (9)

1. a toughen and intensify environment-friendly flame retardant PBT and PET alloy, it is characterized in that, its component by mass percent proportioning is: PBT 20% ~ 60%, PET 10% ~ 40%, glass fibre 10% ~ 25%, halogen-free flame retardants 5% ~ 15%, nano-calcium carbonate 5% ~ 15%, elastomerics 5% ~ 10%, maleic anhydride 0.5% ~ 2%, diethyl azodiformate 0.1% ~ 1%, softening agent 1% ~ 5%, composite nucleating agent 0.1% ~ 1%, composite antioxidant 0.1% ~ 1%, lubricant 0.1% ~ 2%.

2. toughen and intensify environment-friendly flame retardant PBT according to claim 1 and PET alloy, is characterized in that, described glass fibre is the alkali free glass fibre of surface through silane coupling agent process.

3. toughen and intensify environment-friendly flame retardant PBT according to claim 1 and PET alloy, it is characterized in that, described halogen-free flame retardants is that organophosphorous fire retardant comprises phosphate flame retardant, phosphorous acid ester fire retardant, phosphonate fire retardant, organophosphorated salt fire retardant, silicone flame retardant comprises polysilane fire retardant, polysiloxane fire retardant, poly organic silicon silsesquioxane fire retardant, and nitrogenated flame retardant comprises one or more the mixture above-mentioned of melamine flame retardants, melamine cyanurate fire retardant.

4. toughen and intensify environment-friendly flame retardant PBT according to claim 1 and PET alloy, is characterized in that, described elastomerics is ethylene-octene copolymer (POE).

5. toughen and intensify environment-friendly flame retardant PBT according to claim 1 and PET alloy, is characterized in that, described softening agent is polyoxyethylene glycol (PEG).

6. toughen and intensify environment-friendly flame retardant PBT according to claim 1 and PET alloy, is characterized in that, described composite nucleating agent is the compound of Sodium Benzoate and ethylene-methyl methacrylate sodium ion polymkeric substance.

7. toughen and intensify environment-friendly flame retardant PBT according to claim 1 and PET alloy, is characterized in that, described composite antioxidant is the compound of hindered phenol antioxygen 1076 and phosphite ester kind antioxidant 168.

8. toughen and intensify environment-friendly flame retardant PBT according to claim 1 and PET alloy, is characterized in that, described lubricant is TAS-2A or ethylene bis stearic amide (EBS).

9. the preparation method of toughen and intensify environment-friendly flame retardant PBT according to claim 1 and PET alloy, is characterized in that, comprise the following steps:

(1), by PBT at 130 DEG C ~ 140 DEG C dry 3 ~ 5 hours, PET at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, halogen-free flame retardants at 60 DEG C ~ 80 DEG C dry 30 ~ 45 minutes, nano-calcium carbonate at 60 DEG C ~ 80 DEG C dry 30 ~ 45 minutes, stand-by;

(2), taking dry nano-calcium carbonate by weight ratio, to add barrel temperature be in 30 DEG C ~ 80 DEG C high-speed mixers, stir 3 ~ 15 minutes, then the maleic anhydride and diethyl azodiformate that take by weight ratio is added, stir 10 ~ 30 minutes, obtain pretreated nano-calcium carbonate, discharging; Again on 50 DEG C ~ 80 DEG C opening rubber mixing machines by pretreated nano-calcium carbonate and the direct mixed milling of elastomerics that claims by weight ratio even, slice, cooling is broken, the core-shell particles that to obtain take nano-calcium carbonate as core, elastomerics is shell, stand-by;

(3), dry PBT, PET and halogen-free flame retardants is taken by weight ratio, add in high-speed mixer and mix 2 ~ 5 minutes, add the core-shell particles that step (2) obtains again, add the softening agent, composite nucleating agent, composite antioxidant and the lubricant that take by weight ratio simultaneously, continue mixing 5 ~ 30 minutes, make fully to mix rear discharging;

(4), the compound of step (3) is added the main spout of twin screw extruder, the glass fibre taken by weight ratio is added the side spout of twin screw extruder, controlled working temperature is at 210 DEG C ~ 260 DEG C, screw speed 200 ~ 500rpm, through twin screw extruder plasticizing mixing after extrude, cooling granulation, get product.