CN104419144A - Halogen-free flame retardant modified PBT material with elastomer and inorganic powder coating structure - Google Patents

Abstract

The invention discloses a halogen-free flame retardant modified PBT material with an elastomer and an inorganic powder coating structure. The halogen-free flame retardant modified PBT material is prepared from the following components in percentage by mass: 60%-80% of PBT, 8%-12% of inorganic powder, 1%-2% of diisocyanate, 2%-4% of butanediol, 3%-8% of maleic anhydride-grafted ethylene-octylene copolymer (POE-g-MAH), 10%-15% of a halogen-free flame retardant, 0.1%-2% of a dispersant and 0.1%-1% of an antioxidant. Compared with the prior art, the halogen-free flame retardant modified PBT material has the beneficial effects that polyurethane rubber elastomer is generated by stirring, performing addition and polymerizing the diisocyanate and butanediol in a mixer in the presence of inorganic powder and the polyurethane rubber elastomer coats on the surface of the inorganic powder to form a nuclear shell structure which takes inorganic powder as a core and elastomer as a shell, so that the toughness and the rigidity of the PBT are remarkably improved. Meanwhile, the prepared PBT material has excellent flame resistance, achieves UL94V-0, and has no drop melting phenomenon in a combustion process, and has the characteristics such as low smoke, no toxicity and environment friendliness.

Description

There is elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material

Technical field

The present invention relates to technical field of polymer materials, specifically one has elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material.

Background technology

Polybutylene terephthalate (PBT) be a kind of high comprehensive performance and have many uses crystalline polymer, but due to poor fire, the shortcoming such as fragility is large, notched Izod impact strength is low, limit the application of PBT in some field.

Summary of the invention

The object of the present invention is to provide a kind of excellent combination property, halogen-free flame-proof environmental protection performance good there is elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material.

The technical solution adopted for the present invention to solve the technical problems is: have elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material, its component by mass percent proportioning is: PBT 60% ~ 80%, inorganic powder 8% ~ 12%, vulcabond 1% ~ 2%, butyleneglycol 2% ~ 4%, maleic anhydride grafted ethene-octene copolymer (POE-g-MAH) 3% ~ 8%, halogen-free flame retardants 10% ~ 15%, dispersion agent 0.1% ~ 2%, oxidation inhibitor 0.1% ~ 1%.

Described inorganic powder is the mixture of one or more in the calcium carbonate of particle diameter more than 1000 orders, silicon-dioxide, talcum powder, mica and diatomite.

Described halogen-free flame retardants is organic phosphorus flame retardant, silicone flame retardant or nitrogenated flame retardant, wherein, organophosphorous fire retardant comprises phosphate flame retardant, phosphorous acid ester fire retardant, phosphonate fire retardant and organophosphorated salt fire retardant, silicone flame retardant comprises polysilane fire retardant, polysiloxane fire retardant and poly organic silicon silsesquioxane fire retardant, and nitrogenated flame retardant comprises melamine flame retardants and melamine cyanurate fire retardant.

Described dispersion agent is the mixture of one or more in polysiloxane, polyethylene wax, Poly Propylene Wax, EVA wax, OP wax, ethylene bis stearic amide (EBS).

Described oxidation inhibitor is the one in the compound of the compound of antioxidant 1010, antioxidant 1076, antioxidant 1010 or antioxidant 1076 and irgasfos 168, antioxidant 1010 or antioxidant 1076 and oxidation inhibitor JC-242.

The above-mentioned preparation method with elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material, comprises the following steps:

(1) by PBT at 120 DEG C ~ 130 DEG C dry 4 ~ 6 hours, moisture control is below 0.03%, stand-by;

(2) by halogen-free flame retardants at 80 DEG C ~ 120 DEG C dry 30 ~ 45 minutes, stand-by;

(3) take inorganic powder and butyleneglycol by weight ratio, add mixing machine stirring at low speed 0.5 ~ 15 minute, and then add vulcabond high-speed stirring 10 ~ 60 minutes at 40 DEG C ~ 70 DEG C temperature, make abundant addition polymerization and coated;

(4) and then add the PBT after taking drying treatment by weight ratio, halogen-free flame retardants and maleic anhydride grafted ethene-octene copolymer (POE-g-MAH), dispersion agent, oxidation inhibitor, high-speed mixing stirs 3 ~ 10 minutes;

(5) more above-mentioned compound is added in twin screw extruder, control screw speed at 120 ~ 600 revs/min, barrel zone temperature, at 190 DEG C ~ 255 DEG C, carries out extruding through twin screw extruder, namely obtains after granulation and of the present inventionly have elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material.

The invention has the beneficial effects as follows, compared with prior art, the present invention adopts inorganic powder to stir in mixing machine through vulcabond and butyleneglycol and addition polymerization generates urethanes elastomerics and at inorganic powder Surface coating, being formed with inorganic powder is core, elastomerics is the nucleocapsid structure of shell, toughness and rigidity can be significantly improved to PBT, simultaneously obtained PBT material has excellent flame retardant properties, reach UL94V-0, and drip phenomenon without melting and there is low cigarette in combustion, nontoxic, the characteristics such as environmental protection, its high comprehensive performance, good processability, dimensional stabilizing, cost is low, electronic apparatus can be widely used in, auto parts machinery, the fields such as mechanical component.

Embodiment

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

Embodiment 1:

One has elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material, and its component by mass percent proportioning is: PBT 67%, the particle diameter calcium carbonate 10% more than 1000 orders, vulcabond 1.5%, butyleneglycol 3%, maleic anhydride grafted ethene-octene copolymer (POE-g-MAH) 5%, phosphate flame retardant 12%, polysiloxane 1%, antioxidant 1010 0.5%.

Preparation method: (1), by PBT at 120 DEG C ~ 130 DEG C dry 4 ~ 6 hours, moisture control is below 0.03%, stand-by; (2) by phosphate flame retardant at 80 DEG C ~ 120 DEG C dry 30 ~ 45 minutes, stand-by; (3) calcium carbonate of particle diameter more than 1000 orders and butyleneglycol is taken by weight ratio, add mixing machine stirring at low speed 0.5 ~ 15 minute, and then add vulcabond high-speed stirring 10 ~ 60 minutes at 40 DEG C ~ 70 DEG C temperature, make abundant addition polymerization and coated; (4) and then add the PBT after taking drying treatment by weight ratio, phosphate flame retardant and maleic anhydride grafted ethene-octene copolymer (POE-g-MAH), polysiloxane, antioxidant 1010, high-speed mixing stirs 3 ~ 10 minutes; (5) more above-mentioned compound is added in twin screw extruder, control screw speed at 120 ~ 600 revs/min, barrel zone temperature, at 190 DEG C ~ 255 DEG C, carries out extruding through twin screw extruder, namely obtains after granulation and of the present inventionly have elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material.

Embodiment 2:

One has elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material, and its component by mass percent proportioning is: the compound 0.5% of PBT 60%, the particle diameter silica 1 2% more than 1000 orders, vulcabond 2%, butyleneglycol 4%, maleic anhydride grafted ethene-octene copolymer (POE-g-MAH) 5%, polysilane fire retardant 15%, polysiloxane 1.5%, antioxidant 1076 and irgasfos 168.

Preparation method: (1), by PBT at 120 DEG C ~ 130 DEG C dry 4 ~ 6 hours, moisture control is below 0.03%, stand-by; (2) by polysilane fire retardant at 80 DEG C ~ 120 DEG C dry 30 ~ 45 minutes, stand-by; (3) silicon-dioxide of particle diameter more than 1000 orders and butyleneglycol is taken by weight ratio, add mixing machine stirring at low speed 0.5 ~ 15 minute, and then add vulcabond high-speed stirring 10 ~ 60 minutes at 40 DEG C ~ 70 DEG C temperature, make abundant addition polymerization and coated; (4) and then add the compound of the PBT after taking drying treatment by weight ratio, polysilane fire retardant and maleic anhydride grafted ethene-octene copolymer (POE-g-MAH), polysiloxane, antioxidant 1076 and irgasfos 168, high-speed mixing stirs 3 ~ 10 minutes; (5) more above-mentioned compound is added in twin screw extruder, control screw speed at 120 ~ 600 revs/min, barrel zone temperature, at 190 DEG C ~ 255 DEG C, carries out extruding through twin screw extruder, namely obtains after granulation and of the present inventionly have elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material.

Embodiment 3:

One has elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material, and its component by mass percent proportioning is: the compound 0.2% of PBT 75%, the particle diameter talcum powder 8% more than 1000 orders, vulcabond 1%, butyleneglycol 2%, maleic anhydride grafted ethene-octene copolymer (POE-g-MAH) 3%, phosphonate fire retardant 10%, ethylene bis stearic amide (EBS) 0.8%, antioxidant 1010 and oxidation inhibitor JC-242.

Preparation method: (1), by PBT at 120 DEG C ~ 130 DEG C dry 4 ~ 6 hours, moisture control is below 0.03%, stand-by; (2) by phosphonate fire retardant at 80 DEG C ~ 120 DEG C dry 30 ~ 45 minutes, stand-by; (3) talcum powder of particle diameter more than 1000 orders and butyleneglycol is taken by weight ratio, add mixing machine stirring at low speed 0.5 ~ 15 minute, and then add vulcabond high-speed stirring 10 ~ 60 minutes at 40 DEG C ~ 70 DEG C temperature, make abundant addition polymerization and coated; (4) and then add the compound of the PBT after taking drying treatment by weight ratio, phosphonate fire retardant and maleic anhydride grafted ethene-octene copolymer (POE-g-MAH), ethylene bis stearic amide (EBS), antioxidant 1010 and oxidation inhibitor JC-242, high-speed mixing stirs 3 ~ 10 minutes; (5) more above-mentioned compound is added in twin screw extruder, control screw speed at 120 ~ 600 revs/min, barrel zone temperature, at 190 DEG C ~ 255 DEG C, carries out extruding through twin screw extruder, namely obtains after granulation and of the present inventionly have elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material.

Claims (6)

1. one kind has elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material, it is characterized in that, its component by mass percent proportioning is: PBT 60% ~ 80%, inorganic powder 8% ~ 12%, vulcabond 1% ~ 2%, butyleneglycol 2% ~ 4%, maleic anhydride grafted ethene-octene copolymer (POE-g-MAH) 3% ~ 8%, halogen-free flame retardants 10% ~ 15%, dispersion agent 0.1% ~ 2%, oxidation inhibitor 0.1% ~ 1%.

2. according to claim 1 have elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material, it is characterized in that, described inorganic powder is the mixture of one or more in the calcium carbonate of particle diameter more than 1000 orders, silicon-dioxide, talcum powder, mica and diatomite.

3. according to claim 1 have elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material, it is characterized in that, described halogen-free flame retardants is organic phosphorus flame retardant, silicone flame retardant or nitrogenated flame retardant, wherein, organophosphorous fire retardant comprises phosphate flame retardant, phosphorous acid ester fire retardant, phosphonate fire retardant and organophosphorated salt fire retardant, silicone flame retardant comprises polysilane fire retardant, polysiloxane fire retardant and poly organic silicon silsesquioxane fire retardant, nitrogenated flame retardant comprises melamine flame retardants and melamine cyanurate fire retardant.

4. according to claim 1 have elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material, it is characterized in that, described dispersion agent is the mixture of one or more in polysiloxane, polyethylene wax, Poly Propylene Wax, EVA wax, OP wax, ethylene bis stearic amide (EBS).

5. according to claim 1 have elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material, it is characterized in that, described oxidation inhibitor is the one in the compound of the compound of antioxidant 1010, antioxidant 1076, antioxidant 1010 or antioxidant 1076 and irgasfos 168, antioxidant 1010 or antioxidant 1076 and oxidation inhibitor JC-242.

6. the preparation method with elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material according to claim 1, is characterized in that, comprise the following steps:

(1) by PBT at 120 DEG C ~ 130 DEG C dry 4 ~ 6 hours, moisture control is below 0.03%, stand-by;

(2) by halogen-free flame retardants at 80 DEG C ~ 120 DEG C dry 30 ~ 45 minutes, stand-by;

(3) take inorganic powder and butyleneglycol by weight ratio, add mixing machine stirring at low speed 0.5 ~ 15 minute, and then add vulcabond high-speed stirring 10 ~ 60 minutes at 40 DEG C ~ 70 DEG C temperature, make abundant addition polymerization and coated;

(4) and then add the PBT after taking drying treatment by weight ratio, halogen-free flame retardants and maleic anhydride grafted ethene-octene copolymer (POE-g-MAH), dispersion agent, oxidation inhibitor, high-speed mixing stirs 3 ~ 10 minutes;

(5) more above-mentioned compound is added in twin screw extruder, control screw speed at 120 ~ 600 revs/min, barrel zone temperature, at 190 DEG C ~ 255 DEG C, carries out extruding through twin screw extruder, namely obtains after granulation and of the present inventionly have elastomerics and inorganic powder clad structure and halogen-free flameproof modified PBT material.