CN103756269A - High temperature-resistant halogen-free flame retardant PBT (polybutylece terephthalate) material and preparation method thereof - Google Patents
High temperature-resistant halogen-free flame retardant PBT (polybutylece terephthalate) material and preparation method thereof Download PDFInfo
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- CN103756269A CN103756269A CN201310748772.9A CN201310748772A CN103756269A CN 103756269 A CN103756269 A CN 103756269A CN 201310748772 A CN201310748772 A CN 201310748772A CN 103756269 A CN103756269 A CN 103756269A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention relates to the technical field of PBT modification, and especially relates to a high temperature-resistant halogen-free flame retardant PBT material and a preparation method thereof. Substances used in the invention, such as phenyl aluminum hypophosphite, nano calcium carbonate, ground calcium carbonate, substituted aryl phosphate salt and pentaerythritol stearate, all have the function of nucleating agent, so that crystal structure of PBT is completed, degree of crystallinity of PBT is increased, and mechanical property and high temperature resistance of PBT are improved. According to the invention, a hypophosphite type inorganic halogen-free flame retardant, as the phenyl aluminum hypophosphite, is used, and the flame retardant plays its function of nucleating agent while retarding flaming, which is beneficial for improvement of mechanical property and heat resistance; phenyl aluminum hypophosphite and antimonous oxide are used in compounded form, so that generation and accumulation of free carbon are reduced, and flame retardance of PBT is enhanced. In a word, by a complete formula system, the produced product has good high temperature resistance, flame retardance and mechanical property. The PBT material can be produced by simple technology, and is low-cost.
Description
Technical field
The present invention relates to PBT modification technology field, particularly relate to a kind of high temperature resistant halogen-free flame-retardant PBT material and preparation method thereof.
Background technology
Polyethylene terephthalate (PBT) has cheap, has good processing characteristics, mechanical property, heat-resistant aging, solvent resistance, water stability,, the characteristics such as electric property, therefore, the 60's of 20th century have just started the application and development as engineering plastics.PBT engineering plastics have been applied to the industries such as automobile, motor, electronics, household electrical appliance and machinery at present.
In traditional PBT plastic engineering, because the flame retardant properties of PBT is not good, therefore need to add fire retardant and strengthen its flame retardant properties.Halogen containing polymers or have good flame retardant properties with the flame-retardant mixture that halogen containing flame-retardant combines, Zeng Zuowei fire retardant material is widely used.But when fire occurs, this class Halogen fire retardant material can produce a large amount of smog and poisonous corrosive hydrogen halides gas, cause secondary harm.New halogen-free flame-retardant system is mainly take phosphorus series compound and metal hydroxides as main, although the amount of being fuming is little during its burning, do not produce poisonous, corrosive gases, has that resistance to elevated temperatures is poor, poor mechanical property, flame retardant resistance do not reach the problem of requirement.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of high temperature resistant halogen-free flame-retardant PBT material is provided, this kind high temperature resistant halogen-free flame-retardant PBT material resistance to elevated temperatures is good, flame retardant properties is good, mechanical property is good, and the preparation method of this invention is simple, and cost is low.
The object of the present invention is achieved like this:
A kind of high temperature resistant halogen-free flame-retardant PBT material, it is comprised of the raw material of following weight part:
PBT resin 60-80 part
Phenyl hypo-aluminum orthophosphate 15-20 part
Antimonous oxide 3-5 part
Ethylene-methyl acrylate copolymer 5-10 part
Nano-calcium carbonate 1-4 part
Water-ground limestone 4-8 part
Substituted aryl phosphate ester salt 1-3 part
Pentaerythritol stearate 0.2-1 part
Tyox B 0.2-1 part.
Preferably, it is comprised of the raw material of following weight part:
PBT resin 65-75 part
Phenyl hypo-aluminum orthophosphate 15-18 part
Antimonous oxide 3-5 part
Ethylene-methyl acrylate copolymer 5-8 part
Nano-calcium carbonate 1-3 part
Water-ground limestone 4-6 part
Substituted aryl phosphate ester salt 1-2 part
Pentaerythritol stearate 0.2-1 part
Tyox B 0.2-1 part.
More preferred, it is comprised of the raw material of following weight part:
65 parts of PBT resins
16 parts of phenyl hypo-aluminum orthophosphates
5 parts of antimonous oxides
7 parts of ethylene-methyl acrylate copolymers
3 parts of nano-calcium carbonates
6 parts of water-ground limestones
2 parts of substituted aryl phosphate ester salts
0.5 part of pentaerythritol stearate
0.5 part of Tyox B.
Wherein, the melting index of described PET resin is 18-22 g/min.PBT of the present invention adopts the product that Changchun, Taiwan model is 1100-211M.
Wherein, in described ethylene-methyl acrylate copolymer, the weight percentage of methyl acrylate is 25%, melt flow rate (MFR) 0.4g/10min.It is the product of AC1125 that the present invention adopts Du Pont's model.
Wherein, the particle diameter of described nano-calcium carbonate is 160-260 nanometer.
Wherein, the particle diameter of described water-ground limestone is 2600-3600 order.
Wherein, described substituted aryl phosphate ester salt adopts the product that Shanxi-Prov Inst of Chemical Industry's model is TMP-5.
A preparation method for high temperature resistant halogen-free flame-retardant PBT material, it comprises following preparation process:
Steps A: PBT resin is toasted to 2-3 hour at 75-80 ℃, standby;
Step B: PBT resin and nano-calcium carbonate, water-ground limestone after baking are added in high-speed mixer, stir, obtain the first mixture;
Step C: add phenyl hypo-aluminum orthophosphate, antimonous oxide, ethylene-methyl acrylate copolymer, substituted aryl phosphate ester salt, pentaerythritol stearate, Tyox B in the first mixture, continue to stir, obtain the second mixture;
Step D: the second mixture is extruded through twin screw extruder, then through cooling, pelletizing, be drying to obtain high temperature resistant halogen-free flame-retardant PBT material.
Wherein, in described step D, the design parameter of twin screw extruder is: a district temperature 198-202 ℃, two 212 ℃ of district's temperature 208 –, three 222 ℃ of district's temperature 218 –, four 232 ℃ of district's temperature 228 –, five 242 ℃ of district's temperature 238 –, six 232 ℃ of district's temperature 228 –, seven 232 ℃ of district's temperature 228 –, screw speed 200-300r/min.
The present invention adopts the fire-retardant reagent of a class inorganic no-halogen of this Hypophosporous Acid, 50 salt of phenyl hypo-aluminum orthophosphate, in fire-retardant, also play nucleator effect, be conducive to the raising of mechanical property and resistance toheat, the composite use of phenyl hypo-aluminum orthophosphate and antimonous oxide, reduce generation and the accumulation of uncombined carbon, strengthened the flame retardant properties of PBT engineering plastics.
Nano-calcium carbonate and water-ground limestone that the present invention adopts both can be used as toughener, can be used as again nucleator.The present invention utilizes little quality and the high surface energy of nano-calcium carbonate, makes nano-calcium carbonate be attached to water-ground limestone surface, form core the composite structure of shell.In mixing process, nano-calcium carbonate is attached to the surface of water-ground limestone along with water-ground limestone moves together, has effectively avoided the agglomeration of nano-calcium carbonate; Because nano-calcium carbonate has high surface energy, it is combined tightr with the macromolecular chain of PBT in addition, and therefore water-ground limestone can be combined with PBT by being attached to its surperficial nano-calcium carbonate, makes PBT surface more smooth, and mechanical property is better; The nano-calcium carbonate that is not attached to water-ground limestone surface will be filled into the various gaps of PBT, shows the various mechanical property advantages of nano material.The mode that the present invention adopts nano-calcium carbonate and water-ground limestone to combine, has reduced cost, has overcome independent use water-ground limestone and nanon calcium carbonatefilled PBT shortcoming, keeps excellent mechanical performances.
The present invention adopts ethylene-methyl acrylate copolymer as toughner, ethylene-methyl acrylate copolymer stability is high, and processing temperature may be up to 300 degree, has polarity and nonpolar functional group, can be good most polymer-compatible, thus the mechanical property of PBT improved.
Nucleator substituted aryl phosphate ester salt can significantly improve rigidity and the transparency of PBT, and PBT is had to good nucleating effect, and the perfect crystalline texture of PBT has increased degree of crystallinity and the crystallization rate of PBT, is conducive to the raising of mechanical property.
The present invention adopts pentaerythritol stearate as lubricant, pentaerythritol stearate has significant high-temperature resistant result, when processing temperature reaches 400 ℃, still can't see obvious decomposing phenomenon, the PBT of partial crystallization is had to fabulous nucleogenesis, can significantly improve transparency and surface smoothness and other mechanical property.Its usage quantity, lower than most of traditional lubricants, can reduce production costs.
The present invention adopts Tyox B as oxidation inhibitor, Tyox B energy hydroperoxide decomposition, produces stable structure, stops oxygenizement, have do not pollute, Undec feature during not painted, high temperature process, be conducive to the raising of mechanical property.
Beneficial effect of the present invention is: phenyl hypo-aluminum orthophosphate, nano-calcium carbonate, water-ground limestone, substituted aryl phosphate ester salt, these materials of pentaerythritol stearate that the present invention adopts all have nucleator effect, the perfect crystalline texture of PBT, increase the degree of crystallinity of PBT, improved its mechanical property and high thermal resistance; The present invention adopts the fire-retardant reagent of a class inorganic no-halogen of this Hypophosporous Acid, 50 salt of phenyl hypo-aluminum orthophosphate, in fire-retardant, also it arrives its nucleator effect, be conducive to the raising of mechanical property and resistance toheat, the composite use of phenyl hypo-aluminum orthophosphate and antimonous oxide, reduce generation and the accumulation of uncombined carbon, strengthened the flame retardant properties of PBT.In a word, the present invention is by a perfect formula system, makes that the product resistance to elevated temperatures that makes is good, flame retardant properties is good, mechanical property is good, and manufacture craft of the present invention is simple, and cost is low.
Embodiment
Below by embodiment, the invention will be further described, but practical range of the present invention is not limited to this.
Embodiment 1.
A kind of high temperature resistant halogen-free flame-retardant PBT material, it is comprised of the raw material of following weight part:
60 parts of PBT resins
15 parts of phenyl hypo-aluminum orthophosphates
3 parts of antimonous oxides
5 parts of ethylene-methyl acrylate copolymers
1 part of nano-calcium carbonate
4 parts of water-ground limestones
1 part of substituted aryl phosphate ester salt
0.2 part of pentaerythritol stearate
0.2 part of Tyox B.
Wherein, the melting index of described PET resin is 18g/min.
Wherein, in described ethylene-methyl acrylate copolymer, the weight percentage of methyl acrylate is 25%, melt flow rate (MFR) 0.4g/10min.
Wherein, the particle diameter of described nano-calcium carbonate is 160 nanometers.
Wherein, the particle diameter of described water-ground limestone is 2600 orders.
Wherein, described substituted aryl phosphate ester salt adopts the product that Shanxi-Prov Inst of Chemical Industry's model is TMP-5.
A preparation method for high temperature resistant halogen-free flame-retardant PBT material, it comprises following preparation process:
Steps A: PBT resin is toasted 2 hours at 75 ℃, standby;
Step B: PBT resin and nano-calcium carbonate, water-ground limestone after baking are added in high-speed mixer, stir, obtain the first mixture;
Step C: add phenyl hypo-aluminum orthophosphate, antimonous oxide, ethylene-methyl acrylate copolymer, substituted aryl phosphate ester salt, pentaerythritol stearate, Tyox B in the first mixture, continue to stir, obtain the second mixture;
Step D: the second mixture is extruded through twin screw extruder, then through cooling, pelletizing, be drying to obtain high temperature resistant halogen-free flame-retardant PBT material.
Wherein, in described step D, the design parameter of twin screw extruder is: 198 ℃ of district's temperature, two 208 ℃ of district's temperature, three 218 ℃ of district's temperature, four 228 ℃ of district's temperature, five 238 ℃ of district's temperature, six 228 ℃ of district's temperature, seven 228 ℃ of district's temperature, screw speed 200r/min.
Embodiment 2.
A kind of high temperature resistant halogen-free flame-retardant PBT material, it is comprised of the raw material of following weight part:
65 parts of PBT resins
16 parts of phenyl hypo-aluminum orthophosphates
5 parts of antimonous oxides
7 parts of ethylene-methyl acrylate copolymers
3 parts of nano-calcium carbonates
6 parts of water-ground limestones
2 parts of substituted aryl phosphate ester salts
0.5 part of pentaerythritol stearate
0.5 part of Tyox B.
Wherein, the melting index of described PET resin is 20g/min.PBT of the present invention adopts the product that Changchun, Taiwan model is 1100-211M.
Wherein, in described ethylene-methyl acrylate copolymer, the weight percentage of methyl acrylate is 25%, melt flow rate (MFR) 0.4g/10min.It is the product of AC1125 that the present invention adopts Du Pont's model.
Wherein, the particle diameter of described nano-calcium carbonate is 200 nanometers.
Wherein, the particle diameter of described water-ground limestone is 3000 orders.
Wherein, described substituted aryl phosphate ester salt adopts the product that Shanxi-Prov Inst of Chemical Industry's model is TMP-5.
A preparation method for high temperature resistant halogen-free flame-retardant PBT material, it comprises following preparation process:
Steps A: PBT resin is toasted 3 hours at 80 ℃, standby;
Step B: PBT resin and nano-calcium carbonate, water-ground limestone after baking are added in high-speed mixer, stir, obtain the first mixture;
Step C: add phenyl hypo-aluminum orthophosphate, antimonous oxide, ethylene-methyl acrylate copolymer, substituted aryl phosphate ester salt, pentaerythritol stearate, Tyox B in the first mixture, continue to stir, obtain the second mixture;
Step D: the second mixture is extruded through twin screw extruder, then through cooling, pelletizing, be drying to obtain high temperature resistant halogen-free flame-retardant PBT material.
Wherein, in described step D, the design parameter of twin screw extruder is: 200 ℃ of district's temperature, two 210 ℃ of district's temperature, three 220 ℃ of district's temperature, four 230 ℃ of district's temperature, five 240 ℃ of district's temperature, six 230 ℃ of district's temperature, seven 230 ℃ of district's temperature, screw speed 250r/min.
Embodiment 3.
A kind of high temperature resistant halogen-free flame-retardant PBT material, it is comprised of the raw material of following weight part:
75 parts of PBT resins
19 parts of phenyl hypo-aluminum orthophosphates
4 parts of antimonous oxides
7 parts of ethylene-methyl acrylate copolymers
4 parts of nano-calcium carbonates
8 parts of water-ground limestones
2 parts of substituted aryl phosphate ester salts
1 part of pentaerythritol stearate
1 part of Tyox B.
Wherein, the melting index of described PET resin is 20g/min.
Wherein, in described ethylene-methyl acrylate copolymer, the weight percentage of methyl acrylate is 25%, melt flow rate (MFR) 0.4g/10min.
Wherein, the particle diameter of described nano-calcium carbonate is 240 nanometers.
Wherein, the particle diameter of described water-ground limestone is 3200 orders.
Wherein, described substituted aryl phosphate ester salt adopts the product that Shanxi-Prov Inst of Chemical Industry's model is TMP-5.
A preparation method for high temperature resistant halogen-free flame-retardant PBT material, it comprises following preparation process:
Steps A: PBT resin is toasted 3 hours at 75 ℃, standby;
Step B: PBT resin and nano-calcium carbonate, water-ground limestone after baking are added in high-speed mixer, stir, obtain the first mixture;
Step C: add phenyl hypo-aluminum orthophosphate, antimonous oxide, ethylene-methyl acrylate copolymer, substituted aryl phosphate ester salt, pentaerythritol stearate, Tyox B in the first mixture, continue to stir, obtain the second mixture;
Step D: the second mixture is extruded through twin screw extruder, then through cooling, pelletizing, be drying to obtain high temperature resistant halogen-free flame-retardant PBT material.
Wherein, in described step D, the design parameter of twin screw extruder is: 202 ℃ of district's temperature, two 208 ℃ of district's temperature, three 220 ℃ of district's temperature, four 232 ℃ of district's temperature, five 238 ℃ of district's temperature, six 232 ℃ of district's temperature, seven 232 ℃ of district's temperature, screw speed 260r/min.
Embodiment 4.
A kind of high temperature resistant halogen-free flame-retardant PBT material, it is comprised of the raw material of following weight part:
80 parts of PBT resins
20 parts of phenyl hypo-aluminum orthophosphates
5 parts of antimonous oxides
10 parts of ethylene-methyl acrylate copolymers
4 parts of nano-calcium carbonates
8 parts of water-ground limestones
3 parts of substituted aryl phosphate ester salts
1 part of pentaerythritol stearate
1 part of Tyox B.
Wherein, the melting index of described PET resin is 22 g/min.
Wherein, in described ethylene-methyl acrylate copolymer, the weight percentage of methyl acrylate is 25%, melt flow rate (MFR) 0.4g/10min.
Wherein, the particle diameter of described nano-calcium carbonate is 260 nanometers.
Wherein, the particle diameter of described water-ground limestone is 3600 orders.
Wherein, described substituted aryl phosphate ester salt adopts the product that Shanxi-Prov Inst of Chemical Industry's model is TMP-5.
A preparation method for high temperature resistant halogen-free flame-retardant PBT material, it comprises following preparation process:
Steps A: PBT resin is toasted 3 hours at 80 ℃, standby;
Step B: PBT resin and nano-calcium carbonate, water-ground limestone after baking are added in high-speed mixer, stir, obtain the first mixture;
Step C: add phenyl hypo-aluminum orthophosphate, antimonous oxide, ethylene-methyl acrylate copolymer, substituted aryl phosphate ester salt, pentaerythritol stearate, Tyox B in the first mixture, continue to stir, obtain the second mixture;
Step D: the second mixture is extruded through twin screw extruder, then through cooling, pelletizing, be drying to obtain high temperature resistant halogen-free flame-retardant PBT material.
Wherein, in described step D, the design parameter of twin screw extruder is: 202 ℃ of district's temperature, two 212 ℃ of district's temperature, three 222 ℃ of district's temperature, four 232 ℃ of district's temperature, five 242 ℃ of district's temperature, six 232 ℃ of district's temperature, seven 232 ℃ of district's temperature, screw speed 300r/min.
Embodiment 1-4 product performance are in Table 1.
Table 1
By table 1, can find out that high temperature resistant halogen-free flame-retardant PBT material resistance to elevated temperatures prepared by the present invention is good, flame retardant properties is good, mechanical property is good.
Finally should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; although the present invention has been done to explain with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify or be equal to replacement technical scheme of the present invention, and not depart from essence and the scope of technical solution of the present invention.
Claims (10)
1. a high temperature resistant halogen-free flame-retardant PBT material, is characterized in that: it is comprised of the raw material of following weight part:
PBT resin 60-80 part
Phenyl hypo-aluminum orthophosphate 15-20 part
Antimonous oxide 3-5 part
Ethylene-methyl acrylate copolymer 5-10 part
Nano-calcium carbonate 1-4 part
Water-ground limestone 4-8 part
Substituted aryl phosphate ester salt 1-3 part
Pentaerythritol stearate 0.2-1 part
Tyox B 0.2-1 part.
2. a kind of high temperature resistant halogen-free flame-retardant PBT material according to claim 1, is characterized in that: it is comprised of the raw material of following weight part:
PBT resin 65-75 part
Phenyl hypo-aluminum orthophosphate 15-18 part
Antimonous oxide 3-5 part
Ethylene-methyl acrylate copolymer 5-8 part
Nano-calcium carbonate 1-3 part
Water-ground limestone 4-6 part
Substituted aryl phosphate ester salt 1-2 part
Pentaerythritol stearate 0.2-1 part
Tyox B 0.2-1 part.
3. a kind of high temperature resistant halogen-free flame-retardant PBT material according to claim 1, is characterized in that: it is comprised of the raw material of following weight part:
65 parts of PBT resins
16 parts of phenyl hypo-aluminum orthophosphates
5 parts of antimonous oxides
7 parts of ethylene-methyl acrylate copolymers
3 parts of nano-calcium carbonates
6 parts of water-ground limestones
2 parts of substituted aryl phosphate ester salts
0.5 part of pentaerythritol stearate
0.5 part of Tyox B.
4. a kind of high temperature resistant halogen-free flame-retardant PBT material according to claim 1, is characterized in that: the melting index of described PET resin is 18-22 g/min.
5. a kind of high temperature resistant halogen-free flame-retardant PBT material according to claim 1, is characterized in that: in described ethylene-methyl acrylate copolymer, the weight percentage of methyl acrylate is 25%, melt flow rate (MFR) 0.4g/10min.
6. a kind of high temperature resistant halogen-free flame-retardant PBT material according to claim 1, is characterized in that: the particle diameter of described nano-calcium carbonate is 160-260 nanometer.
7. a kind of high temperature resistant halogen-free flame-retardant PBT material according to claim 1, is characterized in that: the particle diameter of described water-ground limestone is 2600-3600 order.
8. a kind of high temperature resistant halogen-free flame-retardant PBT material according to claim 1, is characterized in that: described substituted aryl phosphate ester salt adopts the product that Shanxi-Prov Inst of Chemical Industry's model is TMP-5.
9. the preparation method of a kind of high temperature resistant halogen-free flame-retardant PBT material as described in claim 1-8 any one, is characterized in that: it comprises following preparation process:
Steps A: PBT resin is toasted to 2-3 hour at 75-80 ℃, standby;
Step B: PBT resin and nano-calcium carbonate, water-ground limestone after baking are added in high-speed mixer, stir, obtain the first mixture;
Step C: add phenyl hypo-aluminum orthophosphate, antimonous oxide, ethylene-methyl acrylate copolymer, substituted aryl phosphate ester salt, pentaerythritol stearate, Tyox B in the first mixture, continue to stir, obtain the second mixture;
Step D: the second mixture is extruded through twin screw extruder, then through cooling, pelletizing, be drying to obtain high temperature resistant halogen-free flame-retardant PBT material.
10. the preparation method of a kind of high temperature resistant halogen-free flame-retardant PBT material according to claim 9, it is characterized in that: in described step D, the design parameter of twin screw extruder is: a district temperature 198-202 ℃, two 212 ℃ of district's temperature 208 –, three 222 ℃ of district's temperature 218 –, four 232 ℃ of district's temperature 228 –, five 242 ℃ of district's temperature 238 –, six 232 ℃ of district's temperature 228 –, seven 232 ℃ of district's temperature 228 –, screw speed 200-300r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310748772.9A CN103756269B (en) | 2013-12-31 | 2013-12-31 | A kind of high temperature resistant halogen-free flame-retardant PBT material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140652A (en) * | 2014-07-17 | 2014-11-12 | 滁州优胜高分子材料有限公司 | Nanometer environmentally friendly pbt material |
| CN104140651A (en) * | 2014-07-17 | 2014-11-12 | 滁州优胜高分子材料有限公司 | High-temperature-resistant pbt material |
| CN104861595A (en) * | 2015-06-08 | 2015-08-26 | 江苏理工学院 | Halogen-free flame retardant PBT material and preparation method thereof |
| CN105907056A (en) * | 2016-07-04 | 2016-08-31 | 蚌埠市正园电子科技有限公司 | High-temperature-resistant PBT (polybutylene terephthalate) material with epoxy resin adhesiveness and preparation method thereof |
| CN106916362A (en) * | 2015-12-24 | 2017-07-04 | 广州市寅源新材料科技有限公司 | A kind of halogen-free anti-flaming polyolefin resin and preparation method thereof |
| CN110041674A (en) * | 2019-05-14 | 2019-07-23 | 河南省科学院同位素研究所有限责任公司 | A kind of fire retardant PBT with no halogen/HDPE composite |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0959497A (en) * | 1995-08-28 | 1997-03-04 | Matsushita Electric Works Ltd | Pbt resin molding material |
| CN101787184A (en) * | 2009-12-30 | 2010-07-28 | 中国石油化工股份有限公司 | Quickly crystallized polyester engineering plastic and preparation method thereof |
| CN102174247A (en) * | 2011-03-02 | 2011-09-07 | 中国科学技术大学苏州研究院 | Halogen-free flame retardant glass fiber reinforced polyester composite and preparation method thereof |
| CN102952379A (en) * | 2012-12-04 | 2013-03-06 | 上海日之升新技术发展有限公司 | Environment-friendly flame retardant glass fiber reinforced polybutylece terephthalate (PBT) material with high comparative tracking index (CTI) value and high glow wire ignition temperature (GWIT) value and preparation method thereof |
-
2013
- 2013-12-31 CN CN201310748772.9A patent/CN103756269B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0959497A (en) * | 1995-08-28 | 1997-03-04 | Matsushita Electric Works Ltd | Pbt resin molding material |
| CN101787184A (en) * | 2009-12-30 | 2010-07-28 | 中国石油化工股份有限公司 | Quickly crystallized polyester engineering plastic and preparation method thereof |
| CN102174247A (en) * | 2011-03-02 | 2011-09-07 | 中国科学技术大学苏州研究院 | Halogen-free flame retardant glass fiber reinforced polyester composite and preparation method thereof |
| CN102952379A (en) * | 2012-12-04 | 2013-03-06 | 上海日之升新技术发展有限公司 | Environment-friendly flame retardant glass fiber reinforced polybutylece terephthalate (PBT) material with high comparative tracking index (CTI) value and high glow wire ignition temperature (GWIT) value and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140652A (en) * | 2014-07-17 | 2014-11-12 | 滁州优胜高分子材料有限公司 | Nanometer environmentally friendly pbt material |
| CN104140651A (en) * | 2014-07-17 | 2014-11-12 | 滁州优胜高分子材料有限公司 | High-temperature-resistant pbt material |
| CN104140651B (en) * | 2014-07-17 | 2016-08-24 | 滁州优胜高分子材料有限公司 | A kind of high temperature resistant pbt material |
| CN104140652B (en) * | 2014-07-17 | 2016-08-24 | 滁州优胜高分子材料有限公司 | A kind of nano environmental protection pbt material |
| CN104861595A (en) * | 2015-06-08 | 2015-08-26 | 江苏理工学院 | Halogen-free flame retardant PBT material and preparation method thereof |
| CN106243638A (en) * | 2015-06-08 | 2016-12-21 | 江苏理工学院 | A kind of fire retardant PBT with no halogen material |
| CN106243638B (en) * | 2015-06-08 | 2018-04-13 | 江苏理工学院 | A kind of fire retardant PBT with no halogen material |
| CN106916362A (en) * | 2015-12-24 | 2017-07-04 | 广州市寅源新材料科技有限公司 | A kind of halogen-free anti-flaming polyolefin resin and preparation method thereof |
| CN105907056A (en) * | 2016-07-04 | 2016-08-31 | 蚌埠市正园电子科技有限公司 | High-temperature-resistant PBT (polybutylene terephthalate) material with epoxy resin adhesiveness and preparation method thereof |
| CN110041674A (en) * | 2019-05-14 | 2019-07-23 | 河南省科学院同位素研究所有限责任公司 | A kind of fire retardant PBT with no halogen/HDPE composite |
| CN110041674B (en) * | 2019-05-14 | 2021-07-20 | 河南省科学院同位素研究所有限责任公司 | Halogen-free flame-retardant PBT/HDPE composite material |
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Application publication date: 20140430 Assignee: Henan new Mstar Technology Ltd Assignor: Dongguan Song Shen Plastics Technology Co., Ltd. Contract record no.: 2016990000176 Denomination of invention: High temperature-resistant halogen-free flame retardant PBT (polybutylece terephthalate) material and preparation method thereof Granted publication date: 20151209 License type: Exclusive License Record date: 20160504 |
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