CN107446324B - Inorganic nanoparticle reinforced halogen-free flame-retardant PBT (polybutylene terephthalate) material and preparation method thereof - Google Patents
Inorganic nanoparticle reinforced halogen-free flame-retardant PBT (polybutylene terephthalate) material and preparation method thereof Download PDFInfo
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- CN107446324B CN107446324B CN201710649761.3A CN201710649761A CN107446324B CN 107446324 B CN107446324 B CN 107446324B CN 201710649761 A CN201710649761 A CN 201710649761A CN 107446324 B CN107446324 B CN 107446324B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
An inorganic nanoparticle reinforced halogen-free flame retardant PBT material comprising: 75-89 parts of PBT resin, 8-20 parts of liquid halogen-free flame retardant, 1-6 parts of inorganic nanoparticles, 0.1-1 part of antioxidant and 0.1-1 part of lubricant. The preparation method comprises the following steps: (a) dispersing inorganic nano particles in a liquid halogen-free flame retardant in advance by adopting a high-speed centrifuge to form a mixture; (b) mixing PBT resin, an antioxidant and a lubricant; (c) and (c) adding the mixture obtained in the step (a) into an extruder for side feeding, adding the mixture obtained in the step (b) into a double-screw extruder for main feeding, and blending and granulating. The inorganic nano particle reinforced PBT material and the preparation method thereof enable the inorganic nano particles to be uniformly dispersed in a resin system, and ensure that the produced PBT material has excellent reinforcing and flame-retardant effects.
Description
Technical Field
The invention relates to the field of polymer blending and polymer molding processing, and particularly relates to an inorganic nanoparticle reinforced halogen-free flame-retardant PBT material and a preparation method thereof.
Background
Polybutylene terephthalate (PBT) has the advantages of high heat resistance, high toughness, good electrical property, rapid injection molding and the like, and is widely used for parts of electronic and electric appliances, automobile accessories, mechanical equipment, precision instruments and the like. However, the flame retardant grade of the PBT resin is only HB, and the PBT resin is modified by adding a flame retardant to improve the flame retardant property. In view of the disadvantages of halogen flame retardants, WEEE directive and ROSE standard were published in the European Union of 2003, and the use of halogen flame retardants was limited.
Thus, the non-halogenation of PBT flame retardancy has become an important research direction.
Disclosure of Invention
The invention aims to provide an inorganic nanoparticle reinforced halogen-free flame retardant PBT material, which achieves the reinforcing effect through inorganic nanoparticles, but the inorganic nanoparticles are difficult to disperse in a resin system, so the application also provides a preparation method for uniformly dispersing the inorganic nanoparticles in a mixture, and the PBT material produced by the preparation method has excellent reinforcing and flame retardant effects.
In order to achieve the purpose, the invention adopts the following technical scheme:
an inorganic nanoparticle reinforced halogen-free flame retardant PBT material comprises the following components in parts by weight:
preferably, the liquid halogen-free flame retardant is bisphenol a bis (diphenyl phosphate).
Preferably, the phosphorus content in the bisphenol A bis (diphenyl phosphate) is 8-10%.
Preferably, the inorganic nanoparticles are one or two of nano montmorillonite and nano silica.
Preferably, the antioxidant is one or more of triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite and dioctadecyl alcohol pentaerythritol diphosphite.
Preferably, the lubricant is one or more of liquid paraffin, solid paraffin, silane polymer, fatty acid salt, fatty acid amide, zinc stearate, calcium stearate, stearic acid amide, methylene bis stearic acid amide, and N, N-ethylene bis stearic acid amide.
A method for preparing the inorganic nanoparticle reinforced halogen-free flame retardant PBT material comprises the following steps:
(a) dispersing inorganic nano particles in a liquid halogen-free flame retardant in advance by adopting a high-speed centrifuge to form a mixture;
(b) mixing PBT resin, an antioxidant and a lubricant;
(c) and (c) adding the mixture obtained in the step (a) into an extruder for side feeding, adding the mixture obtained in the step (b) into a double-screw extruder for main feeding, and blending and granulating.
Preferably, the PBT resin has an intrinsic viscosity of 0.8-1.0.
Preferably, said step (b) uses a mixer-blender.
Preferably, said step (c) uses a twin-screw extruder.
The invention has the beneficial effects that:
the inorganic nano particle reinforced PBT material and the preparation method thereof enable the inorganic nano particles to be uniformly dispersed in a resin system, and ensure that the produced PBT material has excellent reinforcing and flame-retardant effects.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
An inorganic nanoparticle reinforced halogen-free flame retardant PBT material comprises the following components in parts by weight:
compared with polyethylene terephthalate (PET) resin, the PBT resin is the polybutylene terephthalate resin, and the-CH 2-chain of the polybutylene terephthalate (PBT) resin is increased, so that the molecular chain is easy to flex, the glass transition temperature is lower than that of the PET, the crystallization speed is increased, and the polybutylene terephthalate resin is easy to mold and process. Is superior to the PBT resin product applied to the fields of electronic appliances, automobile parts, mechanical equipment, precision instruments and the like, and adds the halogen-free flame retardant in order to ensure that the PBT resin achieves better flame retardant effect. However, the halogen-free flame retardant PBT has low impact strength and poor toughness, and for some parts with higher toughness requirements, such as parts comprising buckles and screw holes, the halogen-free flame retardant PBT cannot meet the use requirements thereof, so that a mode of adding inorganic nanoparticles for reinforcing and toughening is adopted.
Preferably, the liquid halogen-free flame retardant is bisphenol a bis (diphenyl phosphate).
Bisphenol a bis (diphenyl phosphate), BDP, is an excellent flame retardant.
Preferably, the phosphorus content in the bisphenol A bis (diphenyl phosphate) is 8-10%.
Preferably, the inorganic nanoparticles are one or two of nano montmorillonite and nano silica.
The particles of the nano material are small, so that the enhancement effect of the prepared PBT modified material is better.
Preferably, the antioxidant is one or more of triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite and dioctadecyl alcohol pentaerythritol diphosphite.
The antioxidant is prepared from a commercially available product, and has the function of improving the aging resistance of the prepared alloy material.
Preferably, the lubricant is one or more of liquid paraffin, solid paraffin, silane polymer, fatty acid salt, fatty acid amide, zinc stearate, calcium stearate, stearic acid amide, methylene bis stearic acid amide, and N, N-ethylene bis stearic acid amide.
Organic lubricants are primarily referred to herein. The addition of the organic lubricant can improve the friction force and the adhesion between particles of each layer of plastic and the metal surface of processing equipment, increase the fluidity of a resin mixing system, achieve the purpose of regulating and controlling the resin plasticizing time and keep the continuous production of extrusion molding.
A method for preparing the inorganic nanoparticle reinforced halogen-free flame retardant PBT material comprises the following steps:
(a) dispersing inorganic nano particles in a liquid halogen-free flame retardant in advance by adopting a high-speed centrifuge to form a mixture;
(b) mixing PBT resin, an antioxidant and a lubricant;
(c) and (c) adding the mixture obtained in the step (a) into an extruder for side feeding, adding the mixture obtained in the step (b) into a double-screw extruder for main feeding, and blending and granulating.
The inorganic nanoparticles are pre-dispersed in the liquid halogen-free flame retardant, so that the inorganic nanoparticles form better dispersion in the halogen-free flame retardant PBT material, and the reinforcing effect of the inorganic nanoparticles on the halogen-free flame retardant PBT material is improved. However, the inorganic nanoparticles are very small in particle size, so that the inorganic nanoparticles are difficult to disperse, and the inorganic nanoparticles can be uniformly dispersed in the halogen-free flame-retardant PBT system by adopting a high-speed centrifuge, so that the strength of the PBT modified material is enhanced practically.
Preferably, the PBT resin has an intrinsic viscosity of 0.8-1.0.
In order to ensure that the inorganic nanoparticles can be sufficiently and uniformly stirred in the mixture, the vertical intrinsic viscosity of the PBT is controlled between the ranges, and the PBT is neither too thick so as to be difficult to stir, nor too thin so as to be difficult to mold.
Preferably, said step (b) uses a mixer-blender.
Preferably, said step (c) uses a twin-screw extruder.
The double-screw extruder has good mixing and plasticizing capacity, short material retention time in the extruder, high yield, high extrusion speed, and low energy consumption per unit yield
Example 1
Preparing the following components in parts by mass:
the preparation method comprises the following steps:
(a) dispersing inorganic nano particles in a liquid halogen-free flame retardant in advance by adopting a high-speed centrifuge to form a mixture;
(b) adding the PBT resin, the antioxidant and the lubricant into a mixing stirrer for mixing for 10 minutes;
(c) and (c) adding the mixture obtained in the step (a) into a double-screw extruder through a liquid feeding pump for side feeding, adding the mixture obtained in the step (b) into the double-screw extruder for main feeding, and performing blending granulation.
Comparative example 1
Preparing the following components in parts by mass:
the preparation method comprises the following steps:
(a) adding the PBT resin, the inorganic nano particles, the antioxidant and the lubricant into a mixing stirrer for mixing for 10 minutes;
(b) and (b) adding the mixture obtained in the step (a) into a double-screw extruder for main feeding, adding the liquid halogen-free flame retardant into the double-screw extruder through a liquid feeding pump for side feeding, and performing blending granulation.
Effect 1
The inorganic nanoparticle reinforced halogen-free flame retardant PBT material prepared in the above example 1 and the comparative example 1 is subjected to injection molding of an impact spline according to the ISO179 standard requirement, and the notched impact strength and unnotched impact strength of the simply supported beam are tested, and detailed results are shown in Table 1.
TABLE 1 comparison of impact strength of example 1 and comparative example 1
| Test items | Test standard | Test conditions | Unit of | Example 1 | Comparative example 1 |
| Impact strength of simply supported beam notch | ISO179 | 23℃ | KJ/m2 | 5.3 | 3.2 |
| Unnotched impact strength | ISO179 | 23℃ | KJ/m2 | 47.5 | 23.8 |
As can be seen from Table 1, using the same parts by mass of the components, if the inorganic nanoparticles are pre-dispersed in the liquid halogen-free flame retardant and other materials such as PBT resin are separately mixed, the two mixtures are blended during extrusion (i.e., example 1), and compared with mixing all the raw materials together and extruding for granulation (i.e., comparative example 1), the former has a higher notched impact strength for the beam than the latter, while the former has a greater notched impact strength for the latter.
Example 3
Preparing the following components in parts by mass:
the preparation method comprises the following steps:
(a) dispersing inorganic nano particles in a liquid halogen-free flame retardant in advance by adopting a high-speed centrifuge to form a mixture;
(b) adding the PBT resin, the antioxidant and the lubricant into a mixing stirrer for mixing for 5 minutes;
(c) and (c) adding the mixture obtained in the step (a) into a double-screw extruder through a liquid feeding pump for side feeding, adding the mixture obtained in the step (b) into the double-screw extruder for main feeding, and performing blending granulation.
Example 4
Preparing the following components in parts by mass:
the preparation method comprises the following steps:
(a) dispersing inorganic nano particles in a liquid halogen-free flame retardant in advance by adopting a high-speed centrifuge to form a mixture;
(b) adding the PBT resin, the antioxidant and the lubricant into a mixing stirrer for mixing for 20 minutes;
(c) and c, adding the mixture obtained in the step a into a double-screw extruder through a liquid feeding pump for side feeding, adding the mixture obtained in the step b into the double-screw extruder for main feeding, and blending and granulating.
Effect of implementation 2
The inorganic nanoparticle reinforced halogen-free flame retardant PBT material prepared in the above examples 3-4 is subjected to injection molding of an impact spline according to the ISO179 standard requirement, and the notched impact strength and unnotched impact strength of the simply supported beam are tested, and detailed results are shown in Table 2.
TABLE 2 comparison of impact strengths of example 3 and example 4
| Test items | Test standard | Test conditions | Unit of | Example 3 | Example 4 |
| Impact strength of simply supported beam notch | ISO179 | 23℃ | KJ/m2 | 3.5 | 4.7 |
| Unnotched impact strength | ISO179 | 23℃ | KJ/m2 | 31.9 | 40.2 |
As can be seen from Table 2, the ratio of the liquid halogen-free flame retardant and the inorganic nanoparticles in the components is increased, and the notch impact strength and the unnotched impact strength of the PBT modified material can be improved by prolonging the mixing and stirring time of the PBT resin, the antioxidant and the lubricant in the step (b).
In conclusion, the method is simple and feasible, and the inorganic nanoparticles are pre-dispersed in the liquid halogen-free flame retardant, so that the inorganic nanoparticles are better dispersed in the halogen-free flame retardant PBT material, and the reinforcing effect of the inorganic nanoparticles on the halogen-free flame retardant PBT material is improved.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (9)
1. The preparation method of the inorganic nanoparticle reinforced halogen-free flame retardant PBT material is characterized by comprising the following steps:
(a) dispersing inorganic nano particles in a liquid halogen-free flame retardant in advance by adopting a high-speed centrifuge to form a mixture;
(b) mixing PBT resin, an antioxidant and a lubricant;
(c) adding the mixture obtained in the step (a) into a double-screw extruder for side feeding, adding the mixture obtained in the step (b) into the double-screw extruder for main feeding, and performing blending granulation;
the halogen-free flame-retardant PBT material comprises the following components in parts by weight:
2. the preparation method of the inorganic nanoparticle reinforced halogen-free flame retardant PBT material according to claim 1, characterized in that: the liquid halogen-free flame retardant is bisphenol A bis (diphenyl phosphate).
3. The preparation method of the inorganic nanoparticle reinforced halogen-free flame retardant PBT material according to claim 2, characterized in that: the phosphorus content in the bisphenol A bis (diphenyl phosphate) is 8-10%.
4. The preparation method of the inorganic nanoparticle reinforced halogen-free flame retardant PBT material according to claim 1, characterized in that: the inorganic nano particles are one or two of nano montmorillonite and nano silicon dioxide.
5. The method for preparing the inorganic nanoparticle reinforced halogen-free flame retardant PBT material according to claim 1, wherein the antioxidant is one or more of triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite, and dioctadecyl alcohol pentaerythritol diphosphite.
6. The method for preparing the inorganic nanoparticle reinforced halogen-free flame retardant PBT material according to claim 1, wherein the lubricant is one or more of liquid paraffin, solid paraffin, silane polymer, fatty acid salt and fatty acid amide.
7. The preparation method of the inorganic nanoparticle reinforced halogen-free flame retardant PBT material of claim 6, wherein the fatty acid salt comprises: one or more of zinc stearate and calcium stearate;
the fatty acid amide is one or more of stearic acid amide, methylene bis-stearic acid amide and N, N' -ethylene bis-stearic acid amide.
8. The preparation method of the inorganic nanoparticle reinforced halogen-free flame retardant PBT material according to claim 1, characterized in that: the PBT resin has an intrinsic viscosity of 0.8-1.0.
9. The method for preparing the inorganic nanoparticle reinforced halogen-free flame retardant PBT material of claim 1, wherein the step (b) uses a mixer.
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| JP2004307546A (en) * | 2003-04-02 | 2004-11-04 | Asahi Fiber Glass Co Ltd | Thermoplastic polyester resin composition |
| CN100506911C (en) * | 2007-01-09 | 2009-07-01 | 南通星辰合成材料有限公司 | Super high flowing, white, fire retardant PBT with no halogen, in high thermal stability, and preparation method |
| JP5286778B2 (en) * | 2007-09-27 | 2013-09-11 | 東レ株式会社 | Flame retardant resin composition |
| CN102295829A (en) * | 2011-05-25 | 2011-12-28 | 深圳市亚塑科技有限公司 | High heating transformative halogen free flame retardant material and its preparation method |
| CN102424716B (en) * | 2011-08-30 | 2014-04-30 | 广东威林工程塑料有限公司 | High-glow wire ignition temperature flame-retardant reinforced polybutylece terephthalate (PBT) material and preparation method thereof |
| CN103709616A (en) * | 2012-09-28 | 2014-04-09 | 青岛欣展塑胶有限公司 | Nanoscale halogen-free flame-retardant PBT composite material |
| CN103205017A (en) * | 2013-03-21 | 2013-07-17 | 深圳市亚塑科技有限公司 | Halogen-free fire retardant and preparation method of halogen-free fire-retardant PBT (polybutylece terephthalate) composite material |
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