CN104845266A - Flame-retardant impact-resistant modified PET/PTT material and preparation method thereof - Google Patents

Abstract

The invention discloses a flame-retardant impact-resistant modified PET/PTT material and a preparation method thereof. The flame-retardant impact-resistant modified PET/PTT material comprises the following components by mass: 23%-56% of PET, 20%-35% of PTT, 2%-4% of a compatilizer, 0.5%-1% of a nucleating agent, 8%-15% of carbonate calcium particles, 5%-10% of TPU, 0.01%-1% of unsaturated organic acid, 0.01%-0.05% of an initiating agent, 0.1%-0.5% of an antioxidant, 0.1%-1% of a lubricant, and 6%-10% of a flame retardant. The flame-retardant impact-resistant modified PET/PTT material provided by the invention integrates the respective advantages of PET and PTT, grafting reaction is carried out on carbonate calcium particles and TPU and core-shell particles with calcium carbonate particles coated by TPU are formed, thus greatly improving the notched impact strength, rigidity and heat resistance. Also, the flame-retardant impact-resistant modified PET/PTT material has the characteristics of good flame retardant effect, excellent processability, low cost and wide adaptability.

Description

A kind of flame-protected impact strength modified PET/PTT material and preparation method thereof

Technical field

The present invention relates to technical field of polymer materials, specifically a kind of flame-protected impact strength modified PET/PTT material and preparation method thereof.

Background technology

Polyethylene terephthalate (PET)/Poly(Trimethylene Terephthalate) (PTT) belongs to a kind of novel high molecule plastic, it has excellent over-all properties and chemical resistance etc., thus will have broad application prospects in automobile, electric, the field such as household electrical appliances, fiber.But the notched Izod impact strength of PET/PTT is low, mechanical property is unstable, poor fire etc., will significantly limit its effect.In order to promote the performance of PET/PTT, often needing in PET/PTT, add three components and carrying out modification, be intended to the co-mixing system obtaining having much practical value, to promote its effect and Application Areas better.

Summary of the invention

Flame-protected impact strength modified PET/PTT material that the object of the present invention is to provide a kind of nucleocapsid toughness reinforcing and preparation method thereof.

The technical solution adopted for the present invention to solve the technical problems is: a kind of flame-protected impact strength modified PET/PTT material, and its component by mass percent proportioning is: PET 23% ~ 56%, PTT 20% ~ 35%, compatilizer 2% ~ 4%, nucleator 0.5% ~ 1%, calcium carbonate particles 8% ~ 15%, TPU 5% ~ 10%, unsaturated organic acid 0.01% ~ 1%, initiator 0.01% ~ 0.05%, oxidation inhibitor 0.1% ~ 0.5%, lubricant 0.1% ~ 1%, fire retardant 6% ~ 10%.

Described PET is polyethylene terephthalate.

Described PTT is Poly(Trimethylene Terephthalate).

Described compatilizer is styrene-grafted copolymer-maleic anhydride.

Described nucleator is Sodium Benzoate.

Described calcium carbonate particles is the water-ground limestone that particle diameter is less than 5 μm.

Described TPU is Polyurethane Thermoplastic Elastomer.

Described unsaturated organic acid is the one in vinylformic acid, methacrylic acid, maleic anhydride, α-hydroxyethyl, 2-butylene acid, maleic acid.

Described initiator is the one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), diethyl azodiformate.

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

Described lubricant is pentaerythritol stearate.

Described fire retardant is the one in TDE, melamine cyanurate, dihydroxyphenyl propane-bis-(diphenyl phosphoester), polyphenylene phosphonic acids sulfobenzide ester.

The preparation method of above-mentioned a kind of flame-protected impact strength modified PET/PTT material, comprises the following steps:

(1), by PET and PTT in forced air circulation baking oven at 110 DEG C ~ 120 DEG C temperature dry 6 ~ 8 hours, by calcium carbonate particles and fire retardant at 60 DEG C ~ 85 DEG C temperature dry 3 ~ 4 hours, stand-by;

(2), take dry calcium carbonate particles by weight ratio and add barrel temperature in the high-speed mixer of 60 DEG C ~ 80 DEG C, stir 3 ~ 15 minutes, then spray art is adopted to add unsaturated organic acid and initiator by weight ratio, stir 10 ~ 45 minutes, add TPU by weight ratio again, stir 10 ~ 15 minutes, make formation with the core-shell particle of TPU coated caco3 particle, then dry PTT is added by important proportioning, and add oxidation inhibitor and lubricant by weight ratio, make to stir 3 ~ 5 minutes together, after fully mixing, discharging adds twin screw extruder and melt extrudes pelletizing, and after drying, i.e. obtained a kind of nucleocapsid toughened master batch based on PTT,

(3) PET and the fire retardant that, take drying by weight ratio add in super mixer, add the nucleocapsid toughened master batch that step (2) is obtained again, and add compatilizer and nucleator by weight ratio, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds in twin screw extruder, extrudes, cooling granulation at 200 DEG C ~ 280 DEG C after melt blending, then dry, obtain a kind of flame-protected impact strength modified PET/PTT material of the present invention.

The invention has the beneficial effects as follows, the present invention combines PET and PTT advantage separately, and adopt calcium carbonate particles and TPU graft reaction occurs and is formed with the core-shell particle of TPU coated caco3 particle, greatly improve notched Izod impact strength, rigidity and thermotolerance etc., flame retardant effect simultaneously, processing characteristics is excellent, and cost is low, wide adaptability, preparation technology is simple.

Embodiment

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

Embodiment 1:

A kind of flame-protected impact strength modified PET/PTT material, its component by mass percent proportioning is: the compound 0.5% of PET 23%, PTT 35%, styrene-grafted copolymer-maleic anhydride 4%, Sodium Benzoate 1%, calcium carbonate particles 15%, TPU 10%, vinylformic acid 0.95%, Diisopropyl azodicarboxylate 0.05%, antioxidant 1010 and irgasfos 168, pentaerythritol stearate 0.5%, TDE 10%, and described calcium carbonate particles is the water-ground limestone that particle diameter is less than 5 μm.

Preparation method: (1), by PET and PTT in forced air circulation baking oven at 110 DEG C ~ 120 DEG C temperature dry 6 ~ 8 hours, by calcium carbonate particles and TDE at 60 DEG C ~ 85 DEG C temperature dry 3 ~ 4 hours, stand-by, (2), take dry calcium carbonate particles by weight ratio and add barrel temperature in the high-speed mixer of 60 DEG C ~ 80 DEG C, stir 3 ~ 15 minutes, then spray art is adopted to add vinylformic acid and Diisopropyl azodicarboxylate by weight ratio, stir 10 ~ 45 minutes, add TPU by weight ratio again, stir 10 ~ 15 minutes, make formation with the core-shell particle of TPU coated caco3 particle, then dry PTT is added by important proportioning, and add the compound of antioxidant 1010 and irgasfos 168 by weight ratio, pentaerythritol stearate, make to stir 3 ~ 5 minutes together, after fully mixing, discharging adds twin screw extruder and melt extrudes pelletizing, and after drying, i.e. obtained a kind of nucleocapsid toughened master batch based on PTT, (3) PET and the TDE that, take drying by weight ratio add in super mixer, add the nucleocapsid toughened master batch that step (2) is obtained again, and add styrene-grafted copolymer-maleic anhydride and Sodium Benzoate by weight ratio, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds in twin screw extruder, extrudes, cooling granulation at 200 DEG C ~ 280 DEG C after melt blending, then dry, obtain a kind of flame-protected impact strength modified PET/PTT material of the present invention.

Embodiment 2:

A kind of flame-protected impact strength modified PET/PTT material, its component by mass percent proportioning is: PET 56%, PTT 20%, styrene-grafted copolymer-maleic anhydride 3%, Sodium Benzoate 0.5%, calcium carbonate particles 8%, TPU 5%, methacrylic acid 0.45%, 2,2'-Azobis(2,4-dimethylvaleronitrile) 0.05%, antioxidant 1010 0.2%, pentaerythritol stearate 0.8%, polyphenylene phosphonic acids sulfobenzide ester 6%, described calcium carbonate particles is the water-ground limestone that particle diameter is less than 5 μm.

Preparation method: (1), by PET and PTT in forced air circulation baking oven at 110 DEG C ~ 120 DEG C temperature dry 6 ~ 8 hours, by calcium carbonate particles and polyphenylene phosphonic acids sulfobenzide ester at 60 DEG C ~ 85 DEG C temperature dry 3 ~ 4 hours, stand-by, (2), take dry calcium carbonate particles by weight ratio and add barrel temperature in the high-speed mixer of 60 DEG C ~ 80 DEG C, stir 3 ~ 15 minutes, then spray art is adopted to add methacrylic acid and 2,2'-Azobis(2,4-dimethylvaleronitrile) by weight ratio, stir 10 ~ 45 minutes, add TPU by weight ratio again, stir 10 ~ 15 minutes, make formation with the core-shell particle of TPU coated caco3 particle, then dry PTT is added by important proportioning, and add antioxidant 1010 and pentaerythritol stearate by weight ratio, make to stir 3 ~ 5 minutes together, after fully mixing, discharging adds twin screw extruder and melt extrudes pelletizing, and after drying, i.e. obtained a kind of nucleocapsid toughened master batch based on PTT, (3) PET and the polyphenylene phosphonic acids sulfobenzide ester that, take drying by weight ratio add in super mixer, add the nucleocapsid toughened master batch that step (2) is obtained again, and add styrene-grafted copolymer-maleic anhydride and Sodium Benzoate by weight ratio, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds in twin screw extruder, extrude after melt blending at 200 DEG C ~ 280 DEG C, cooling granulation, then dry, obtain a kind of flame-protected impact strength modified PET/PTT material of the present invention.

Claims (8)

1. a flame-protected impact strength modified PET/PTT material, it is characterized in that, its component by mass percent proportioning is: PET 23% ~ 56%, PTT 20% ~ 35%, compatilizer 2% ~ 4%, nucleator 0.5% ~ 1%, calcium carbonate particles 8% ~ 15%, TPU 5% ~ 10%, unsaturated organic acid 0.01% ~ 1%, initiator 0.01% ~ 0.05%, oxidation inhibitor 0.1% ~ 0.5%, lubricant 0.1% ~ 1%, fire retardant 6% ~ 10%.

2. a kind of flame-protected impact strength modified PET/PTT material according to claim 1, it is characterized in that, described compatilizer is styrene-grafted copolymer-maleic anhydride.

3. a kind of flame-protected impact strength modified PET/PTT material according to claim 1, it is characterized in that, described nucleator is Sodium Benzoate.

4. a kind of flame-protected impact strength modified PET/PTT material according to claim 1, it is characterized in that, described calcium carbonate particles is the water-ground limestone that particle diameter is less than 5 μm.

5. a kind of flame-protected impact strength modified PET/PTT material according to claim 1, is characterized in that, described unsaturated organic acid is the one in vinylformic acid, methacrylic acid, maleic anhydride, α-hydroxyethyl, 2-butylene acid, maleic acid.

6. a kind of flame-protected impact strength modified PET/PTT material according to claim 1, it is characterized in that, described initiator is the one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), diethyl azodiformate.

7. a kind of flame-protected impact strength modified PET/PTT material according to claim 1, is characterized in that, described fire retardant is the one in TDE, melamine cyanurate, dihydroxyphenyl propane-bis-(diphenyl phosphoester), polyphenylene phosphonic acids sulfobenzide ester.

8. the preparation method of a kind of flame-protected impact strength modified PET/PTT material according to claim 1, is characterized in that, comprise the following steps:

(1), by PET and PTT in forced air circulation baking oven at 110 DEG C ~ 120 DEG C temperature dry 6 ~ 8 hours, by calcium carbonate particles and fire retardant at 60 DEG C ~ 85 DEG C temperature dry 3 ~ 4 hours, stand-by;

(2), take dry calcium carbonate particles by weight ratio and add barrel temperature in the high-speed mixer of 60 DEG C ~ 80 DEG C, stir 3 ~ 15 minutes, then spray art is adopted to add unsaturated organic acid and initiator by weight ratio, stir 10 ~ 45 minutes, add TPU by weight ratio again, stir 10 ~ 15 minutes, make formation with the core-shell particle of TPU coated caco3 particle, then dry PTT is added by important proportioning, and add oxidation inhibitor and lubricant by weight ratio, make to stir 3 ~ 5 minutes together, after fully mixing, discharging adds twin screw extruder and melt extrudes pelletizing, and after drying, i.e. obtained a kind of nucleocapsid toughened master batch based on PTT,

(3) PET and the fire retardant that, take drying by weight ratio add in super mixer, add the nucleocapsid toughened master batch that step (2) is obtained again, and add compatilizer and nucleator by weight ratio, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds in twin screw extruder, extrudes, cooling granulation at 200 DEG C ~ 280 DEG C after melt blending, then dry, obtain a kind of flame-protected impact strength modified PET/PTT material of the present invention.