CN104845167A - Flame-retardant and reinforced PET/PTT/TPEE composite material - Google Patents

Abstract

The invention provides a flame-retardant and reinforced PET/PTT/TPEE composite material, which comprises the following components in mass percentage: 20-60% of PET, 20-30% of PTT, 5-15% of TPEE, 5-15% of reinforcing agent, 6-10% of halogen-free flame retardant, 3-5% of compatilizer, 0.5-2% of anti-aging agent, 0.5-1% of nucleating agent, 0.1-0.5% of antioxidant, and 0.1-1% of lubricant. The reinforcing agent is in the form of fibrous wollastonite, wherein the surface of the reinforcing agent is modified by a silane coupling agent and the diameter of the fibrous wollastonite is within the range of 3-30 [mu]m. The length of the fibrous wollastonite is within the range of 10-500 [mu]m and the length-diameter ratio of the fibrous wollastonite is within the range of 3-100. According to the invention, the flame-retardant and reinforced PET/PTT/TPEE composite material integrates the original advantages of PET, PTT and TPEE, and is also excellent in mechanical performance and flame-retardant property. The limit oxygen index of the composite material is up to over 35%. Meanwhile, the flame-retardant and reinforced PET/PTT/TPEE composite material meets the halogen-free, environment-friendly, droplet-proof and flame-retardant requirements up to the UL94V-0 level.

Description

Flame-retardant strengthening polythylene terephthalate (PET)/PTT/TPEE matrix material

Technical field

The present invention relates to technical field of polymer materials, specifically a kind of flame-retardant strengthening polythylene terephthalate (PET)/PTT/TPEE matrix material.

Background technology

Polyethylene terephthalate (PET)/Poly(Trimethylene Terephthalate) (PTT) belongs to a kind of novel plastics composite, it has excellent physicochemical property and processing characteristics, and cost is low, thus will have broad application prospects in automobile, electric, the field such as household electrical appliances, fiber.Polyether ester (TPEE) is polybutylene terephthalate-polyethylene oxide-poly(propylene oxide) thermoplastic elastomer, be the segmented copolymer obtained by copolycondensation by dimethyl terephthalate (DMT), butyleneglycol, polyethylene oxide glycol and/or polypropylene oxide glycol, there is good snappiness and mechanical property.By the PET/PTT/TPEE matrix material of blended for PET/PTT and TPEE preparation, can the advantage of comprehensive three well, realize the inaccessiable over-all properties of single variety, but the flame retardant resistance of PET/PTT/TPEE self is bad, the Application Areas of high flame retardant can not be suitable for well.

Summary of the invention

The object of the present invention is to provide a kind of flame-retardant strengthening polythylene terephthalate (PET)/PTT/TPEE matrix material with excellent modified effect.

The technical solution adopted for the present invention to solve the technical problems is: flame-retardant strengthening polythylene terephthalate (PET)/PTT/TPEE matrix material, and its component by mass percent proportioning is: PET 20% ~ 60%, PTT 20% ~ 30%, TPEE 5% ~ 15%, toughener 5% ~ 15%, halogen-free flame retardants 6% ~ 10%, compatilizer 3% ~ 5%, antiager 0.5% ~ 2%, nucleator 0.5% ~ 1%, oxidation inhibitor 0.1% ~ 0.5%, lubricant 0.1% ~ 1%.

Described PET is polyethylene terephthalate.

Described PTT is Poly(Trimethylene Terephthalate).

Described TPEE is polybutylene terephthalate-polyethylene oxide-poly(propylene oxide) triblock copolymer.

Described toughener be surface through silane coupler modified process and diameter 3 ~ 30 μm, length is at 10 ~ 500 μm and the fibrous wollastonite of length-to-diameter ratio in 3 ~ 100 scopes.

Described halogen-free flame retardants is the compound of the polyphenylene phosphonic acids sulfobenzide ester of mass ratio 5:4:1, polydimethylsiloxane and tetrafluoroethylene.

Described compatilizer is ethylene-ethylacrylate-glycidyl methacrylate triblock copolymer.

Described antiager is 2-hydroxyl-4 n-octyloxies-benzophenone or 2,4 dihydroxyl benzophenone.

Described nucleator is the nano silicon of mass ratio 2:1 and the compound of Sodium Benzoate.

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

Described lubricant is the one in calcium stearate, silicone powder, pentaerythritol stearate.

The preparation method of above-mentioned flame-retardant strengthening polythylene terephthalate (PET)/PTT/TPEE matrix 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, stand-by;

(2), 5:4:1 takes polyphenylene phosphonic acids sulfobenzide ester, polydimethylsiloxane and tetrafluoroethylene in mass ratio, and add in super mixer and mix, then at 80 DEG C ~ 85 DEG C temperature dry 30 ~ 45 minutes, described halogen-free flame retardants is namely obtained, stand-by;

(3), taking dry PTT by weight ratio adds in super mixer, add the halogen-free flame retardants that step (2) is obtained more by weight ratio, and add antiager, oxidation inhibitor, lubricant by weight ratio, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds twin screw extruder and melt extrudes pelletizing and after drying, namely obtain a kind of PTT composite master batch;

(4), taking dry PET by weight ratio adds in super mixer, add the PTT composite master batch that step (3) is obtained again, and add TPEE, toughener, compatilizer and nucleator by weight ratio, make to be mixed together 3 ~ 15 minutes, after fully mixing, discharging adds in twin screw extruder, extrudes, cooling granulation at 210 DEG C ~ 280 DEG C after melt blending, then dry, obtain flame-retardant strengthening polythylene terephthalate (PET) of the present invention/PTT/TPEE matrix material.

The invention has the beneficial effects as follows, the present invention combines PET, PTT and TPEE advantage separately, and also have excellent mechanical property and flame retardant properties, its limiting oxygen index(LOI) can reach more than 35%, and meets the flame-retardancy requirements of Halogen, environmental protection, resistance to molten drop and UL94 V-0 level.

Embodiment

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

Embodiment 1:

A kind of flame-retardant strengthening polythylene terephthalate (PET)/PTT/TPEE matrix material, its component by mass percent proportioning is: PET 21%, PTT 30%, TPEE 15%, toughener 15%, halogen-free flame retardants 10%, ethylene-ethylacrylate-glycidyl methacrylate triblock copolymer 5%, 2-hydroxyl-4 n-octyloxies-benzophenone 2%, nucleator 1%, the compound 0.5% of antioxidant 1076 and irgasfos 168, calcium stearate 0.5%, described toughener is that surface is through silane coupler modified process, and diameter is at 3 ~ 30 μm, length is at 10 ~ 500 μm and the fibrous wollastonite of length-to-diameter ratio in 3 ~ 100 scopes, described halogen-free flame retardants is the polyphenylene phosphonic acids sulfobenzide ester of mass ratio 5:4:1, the compound of polydimethylsiloxane and tetrafluoroethylene, described nucleator is the nano silicon of mass ratio 2:1 and the compound of Sodium Benzoate.

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, stand-by; (2), 5:4:1 takes polyphenylene phosphonic acids sulfobenzide ester, polydimethylsiloxane and tetrafluoroethylene in mass ratio, and add in super mixer and mix, then at 80 DEG C ~ 85 DEG C temperature dry 30 ~ 45 minutes, described halogen-free flame retardants is namely obtained, stand-by; (3), taking dry PTT by weight ratio adds in super mixer, add the halogen-free flame retardants that step (2) is obtained more by weight ratio, and add compound, the calcium stearate of 2-hydroxyl-4 n-octyloxies-benzophenone, antioxidant 1076 and irgasfos 168 by weight ratio, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds twin screw extruder and melt extrudes pelletizing and after drying, namely obtain a kind of PTT composite master batch; (4), taking dry PET by weight ratio adds in super mixer, add the PTT composite master batch that step (3) is obtained again, and add TPEE, toughener, ethylene-ethylacrylate-glycidyl methacrylate triblock copolymer, nucleator by weight ratio, make to be mixed together 3 ~ 15 minutes, after fully mixing, discharging adds in twin screw extruder, extrude after melt blending at 210 DEG C ~ 280 DEG C, cooling granulation, then dry, obtain flame-retardant strengthening polythylene terephthalate (PET) of the present invention/PTT/TPEE matrix material.

Embodiment 2:

A kind of flame-retardant strengthening polythylene terephthalate (PET)/PTT/TPEE matrix material, its component by mass percent proportioning is: PET 59%, PTT 20%, TPEE 5%, toughener 5%, halogen-free flame retardants 6%, ethylene-ethylacrylate-glycidyl methacrylate triblock copolymer 3%, 2, 4-dihydroxy benaophenonel 0.5%, nucleator 1%, antioxidant 1010 0.2%, pentaerythritol stearate 0.3%, described toughener is that surface is through silane coupler modified process, and diameter is at 3 ~ 30 μm, length is at 10 ~ 500 μm and the fibrous wollastonite of length-to-diameter ratio in 3 ~ 100 scopes, described halogen-free flame retardants is the polyphenylene phosphonic acids sulfobenzide ester of mass ratio 5:4:1, the compound of polydimethylsiloxane and tetrafluoroethylene, described nucleator is the nano silicon of mass ratio 2:1 and the compound of Sodium Benzoate.

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, stand-by; (2), 5:4:1 takes polyphenylene phosphonic acids sulfobenzide ester, polydimethylsiloxane and tetrafluoroethylene in mass ratio, and add in super mixer and mix, then at 80 DEG C ~ 85 DEG C temperature dry 30 ~ 45 minutes, described halogen-free flame retardants is namely obtained, stand-by; (3), taking dry PTT by weight ratio adds in super mixer, add the halogen-free flame retardants that step (2) is obtained more by weight ratio, and add 2 by weight ratio, 4-dihydroxy benaophenonel, antioxidant 1010, pentaerythritol stearate, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds twin screw extruder and melt extrudes pelletizing and after drying, namely obtain a kind of PTT composite master batch; (4), taking dry PET by weight ratio adds in super mixer, add the PTT composite master batch that step (3) is obtained again, and add TPEE, toughener, ethylene-ethylacrylate-glycidyl methacrylate triblock copolymer, nucleator by weight ratio, make to be mixed together 3 ~ 15 minutes, after fully mixing, discharging adds in twin screw extruder, extrude after melt blending at 210 DEG C ~ 280 DEG C, cooling granulation, then dry, obtain flame-retardant strengthening polythylene terephthalate (PET) of the present invention/PTT/TPEE matrix material.

Claims (7)

1. flame-retardant strengthening polythylene terephthalate (PET)/PTT/TPEE matrix material, it is characterized in that, its component by mass percent proportioning is: PET 20% ~ 60%, PTT 20% ~ 30%, TPEE 5% ~ 15%, toughener 5% ~ 15%, halogen-free flame retardants 6% ~ 10%, compatilizer 3% ~ 5%, antiager 0.5% ~ 2%, nucleator 0.5% ~ 1%, oxidation inhibitor 0.1% ~ 0.5%, lubricant 0.1% ~ 1%.

2. flame-retardant strengthening polythylene terephthalate (PET) according to claim 1/PTT/TPEE matrix material, it is characterized in that, described toughener be surface through silane coupler modified process and diameter 3 ~ 30 μm, length is at 10 ~ 500 μm and the fibrous wollastonite of length-to-diameter ratio in 3 ~ 100 scopes.

3. flame-retardant strengthening polythylene terephthalate (PET) according to claim 1/PTT/TPEE matrix material, is characterized in that, described halogen-free flame retardants is the compound of the polyphenylene phosphonic acids sulfobenzide ester of mass ratio 5:4:1, polydimethylsiloxane and tetrafluoroethylene.

4. flame-retardant strengthening polythylene terephthalate (PET) according to claim 1/PTT/TPEE matrix material, is characterized in that, described compatilizer is ethylene-ethylacrylate-glycidyl methacrylate triblock copolymer.

5. flame-retardant strengthening polythylene terephthalate (PET) according to claim 1/PTT/TPEE matrix material, is characterized in that, described antiager is 2-hydroxyl-4 n-octyloxies-benzophenone or 2,4 dihydroxyl benzophenone.

6. flame-retardant strengthening polythylene terephthalate (PET) according to claim 1/PTT/TPEE matrix material, is characterized in that, described nucleator is the nano silicon of mass ratio 2:1 and the compound of Sodium Benzoate.

7. the preparation method of flame-retardant strengthening polythylene terephthalate (PET) according to claim 1/PTT/TPEE matrix material, 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, stand-by;

(2), 5:4:1 takes polyphenylene phosphonic acids sulfobenzide ester, polydimethylsiloxane and tetrafluoroethylene in mass ratio, and add in super mixer and mix, then at 80 DEG C ~ 85 DEG C temperature dry 30 ~ 45 minutes, described halogen-free flame retardants is namely obtained, stand-by;

(3), taking dry PTT by weight ratio adds in super mixer, add the halogen-free flame retardants that step (2) is obtained more by weight ratio, and add antiager, oxidation inhibitor, lubricant by weight ratio, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds twin screw extruder and melt extrudes pelletizing and after drying, namely obtain a kind of PTT composite master batch;

(4), taking dry PET by weight ratio adds in super mixer, add the PTT composite master batch that step (3) is obtained again, and add TPEE, toughener, compatilizer and nucleator by weight ratio, make to be mixed together 3 ~ 15 minutes, after fully mixing, discharging adds in twin screw extruder, extrudes, cooling granulation at 210 DEG C ~ 280 DEG C after melt blending, then dry, obtain flame-retardant strengthening polythylene terephthalate (PET) of the present invention/PTT/TPEE matrix material.