CN110054889B - Flame-retardant bio-based PA56 composite material and preparation method thereof - Google Patents

Flame-retardant bio-based PA56 composite material and preparation method thereof Download PDF

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CN110054889B
CN110054889B CN201810050126.8A CN201810050126A CN110054889B CN 110054889 B CN110054889 B CN 110054889B CN 201810050126 A CN201810050126 A CN 201810050126A CN 110054889 B CN110054889 B CN 110054889B
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flame
composite material
flame retardant
retardant
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CN110054889A (en
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胡定军
秦兵兵
刘修才
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Cathay Wusu Biomaterial Co ltd
Cathay R&D Center Co Ltd
CIBT America Inc
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Cathay Wusu Biological Material Co ltd
Cathay R&D Center Co Ltd
CIBT America Inc
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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Abstract

The invention provides a flame-retardant bio-based PA56 composite material and a preparation method thereof, wherein the flame-retardant bio-based PA56 composite material comprises 100 parts of bio-based PA56, 5-10 parts of long-chain bio-based PA510, 3-5 parts of a compatibilizer, 10-25 parts of a flame retardant, 3-5 parts of a flame-retardant synergist and 10-30 parts of a reinforcing agent. The flame-retardant bio-based PA56 composite material has high relative tracking index and glow wire temperature, and also has good mechanical properties.

Description

Flame-retardant bio-based PA56 composite material and preparation method thereof
Technical Field
The invention belongs to the field of high polymer materials, and relates to a flame-retardant bio-based PA56 composite material and a preparation method thereof.
Background
Polyamides are often used in automobile parts, parts of electric and electronic equipment, and other many applications because of their excellent mechanical properties and moldability. The polyamide has good flame retardance, belongs to a self-extinguishing material, has good electrical insulation performance (comparative tracking index CTI 600), and is widely applied to electronic and electrical equipment. In electronic and electrical appliance applications, in order to maintain better mechanical properties and flame retardance, glass fibers are generally added into a polyamide matrix for reinforcement modification and a halogen flame retardant is used, based on the premise of meeting ROHS & Reach instruction requirements, the halogen flame retardant is a halogen polymer, generally Brominated Polystyrene (BPS), and compared with phosphorus flame retardants and nitrogen flame retardants, the brominated polystyrene enables a polyamide composite material to have excellent mechanical properties, but due to the addition of the glass fibers and the use of the BPS, the relative electric leakage tracking index and glow wire temperature of the material are reduced. In addition, in these electric and electronic parts, requirements for glow wire properties and arc tracking resistance, as represented by the european IEC specification, are increasing. In particular, with regard to connector parts, the required level of Glow Wire Ignition Temperature (GWIT) in the IEC 60695-2-13 specification has recently been revised from 725 ℃ or higher to 775 ℃ or higher, and sometimes the relative tracking index (CTI) is required to be more than 400V, so that it is necessary to consider a polyamide material that achieves both a high relative tracking index and a high glow wire temperature, as well as good mechanical properties.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the flame-retardant bio-based PA56 composite material with high relative tracking index, high glow wire temperature and good mechanical property, and renewable energy is used as a production raw material, so that the environment is protected.
In order to achieve the above purpose, the solution of the invention is as follows:
a flame retardant bio-based PA56 composite, comprising: bio-based PA56, long-chain bio-based PA510, a compatibilizer, a flame retardant synergist and a reinforcing agent.
In a preferred embodiment of the invention, the relative viscosity of the bio-based PA56 is 2.0-4.0, and the mass part is as follows: 100 parts.
In a preferred embodiment of the present invention, the long-chain bio-based PA510 has a relative viscosity of 2.9, parts by mass: 5-10 parts.
In a preferred embodiment of the invention, the compatibilizer is maleic anhydride grafted polyolefin elastomer MAH-g-POE, and the mass parts are as follows: 3-5 parts.
In a preferred embodiment of the invention, the flame retardant is brominated polystyrene, and the mass parts are as follows: 10-25 parts.
In a preferred embodiment of the invention, the flame-retardant synergist is antimony trioxide, and the mass portion is as follows: 3-5 parts.
In a preferred embodiment of the invention, the reinforcing agent is alkali-free glass fiber, and the mass parts are as follows: 10-30 parts.
In a preferred embodiment of the invention, the flame retardant bio-based PA56 composite material may further include other processing aids, which may be selected from any one or more of compatibilizers, antioxidants, lubricants, and dispersants.
The flame-retardant bio-based PA56 composite material has a Comparative Tracking Index (CTI) of 350-400V and a Glow Wire Ignition Temperature (GWIT) of 800-850 ℃.
The preparation method of the flame-retardant bio-based PA56 composite material comprises the following steps:
1) premixing at least raw material components of a bio-based PA56, a long-chain bio-based PA510, a compatibilizer, a flame retardant and a flame retardant synergist to obtain a first premix;
2) adding the first premix into a double-screw extruder from a main feeding port of the double-screw extruder and adding the reinforcing agent into the double-screw extruder from a side feeding port of the double-screw extruder respectively to obtain a second premix, wherein the length-diameter ratio of a screw of the double-screw extruder is 1:40, the rotating speed of the screw is 200-500 rpm, the temperature of each zone of the double-screw extruder is set to be 80 +/-10 ℃, 220 +/-15 ℃, 250 +/-5 ℃, 270 +/-10 ℃, 280 +/-5 ℃, 280 +/-10 ℃ and 275 +/-15 ℃ from the feeding port to a die orifice in sequence, and the temperature of the die orifice is 270 +/-10 ℃;
3) adding the second premix into a melt mixing machine for melt mixing, wherein the melt mixing temperature is 30-50 ℃ higher than the melting point of the bio-based PA56, and the melt mixing time is 0.25-5 minutes, so as to obtain a melt mixed material;
4) and extruding the molten and mixed material from a nozzle of a melting and mixing machine to obtain a strand material, wherein the temperature of the strand material is 230-350 ℃, then cooling the strand material in water, and cutting the cooled strand material in a granulator to obtain the flame-retardant bio-based PA56 composite material.
Among them, since the strands cannot be cut and rolled directly by a pelletizer, it is necessary to cool them to below the melting point of bio-based PA56 using cooling water.
Experiments show that the polyamide flame-retardant material has good mechanical properties while the relative tracking index and the high glow-wire temperature of the polyamide flame-retardant material can be improved by adding the long-chain polyamide and the maleic anhydride grafted polyolefin elastomer into the existing flame-retardant polyamide system for blending.
The invention has the beneficial effects that:
the invention provides a flame-retardant bio-based PA56 composite material which has high Comparative Tracking Index (CTI) and glow wire temperature and good mechanical properties.
Detailed Description
The invention provides a flame-retardant bio-based PA56 composite material and a preparation method thereof.
[ Bio-based PA56]
PA56 uses at least pentanediamine (biomass source) and adipic acid as production raw materials. Pentanediamines are made by biological fermentation (e.g., by decarboxylation of lysine under the action of a decarboxylase) and contain organic carbon of renewable origin that at least partially meets the ASTM D6866 standard. Specifically, the bio-based polyamide is bio-based PA56, the relative viscosity is 2.0-4.0 and is lower than 2.0, the mechanical property of the material is poor, the relative viscosity is higher than 4.0, the material is difficult to process and form by adopting the existing equipment, and the mass part of the bio-based PA56 is 100 parts.
[ Long-chain Bio-based PA510]
The relative viscosity of the long-chain bio-based PA510 is 2.0-4.0, and in order to obtain a good mixing effect, the ratio of the relative viscosity of the long-chain bio-based PA510 to the relative viscosity of the bio-based PA56 is 1.1: 1-1.3: 1 according to the principle that the equal relative viscosity is easier to disperse and mix.
[ compatibilizers ]
The compatibilizer was a maleic anhydride grafted polyolefin elastomer MAH-g-P0E available from Ningbo energy, Inc. (N406).
[ flame retardant ]
The flame retardant is brominated polystyrene which is purchased from Yabao company (HP-3010) in America, and the mass portion of the flame retardant is 10-25 parts.
[ flame retardant synergist ]
The flame-retardant synergist is antimony trioxide, which is purchased from Huaxinxing antimony Co., Ltd (environment-friendly, content is 99.50%).
[ enhancer ]
The reinforcing agent was alkali-free glass fiber, available from boulder corporation, china (568H).
The present invention will be further described with reference to the following specific examples.
< methods for characterizing Properties >
The following methods were used for performance characterization:
1. determination of the relative viscosity of the polyamides:
measured according to ISO 307.
2. Tensile strength:
measured according to ISO 527-2.
3. Impact strength:
the measurement was carried out according to ISO 180/1A.
4. Relative tracking index (CTI):
test pieces having a length of 100mm, a width of 100mm and a thickness of 3mm were prepared and measured by the method of IEC 60112.
5. Glow Wire (GWIT):
test pieces having a length of 80mm, a width of 80mm and a thickness of 3mm were prepared and measured by the method of IEC 60695-2-13.
6. And (3) testing vertical combustion performance:
test pieces having a length of 12.7mm, a width of 12.7mm and a thickness of 0.8mm were produced and tested in accordance with UL94 specification.
< raw materials for production >
The raw materials for the following examples were as follows:
bio-based PA 56: kaiser (Jinxiang) biomaterial, Inc., having a relative viscosity of 2.7(98 wt% concentrated sulfuric acid process);
long-chain bio-based PA 510: kaiser (Jinxiang) biomaterial, Inc., having a relative viscosity of 3.0(98 wt% concentrated sulfuric acid process);
maleic anhydride grafted polyolefin elastomer (MAH-g-POE): ningbo optical fiber Inc. (N406);
alkali-free glass fiber: china giant stone corporation (568H);
brominated Polystyrene (BPS): yabao corporation, USA (HP-3010);
antimony trioxide (Sb)2O3): huaxing antimony industries, Inc. of Lou bottom of Hunan province (environmental protection type, content is 99.50%).
The preparation method of the flame retardant bio-based PA56 composite material in the examples and the comparative examples comprises the following steps:
1) mixing biological group PA56, long-chain biological group PA510, maleic anhydride grafted polyolefin elastomer MAH-g-POE, brominated polystyrene BPS and antimony trioxide Sb2O3Premixing according to the mixture ratio of the table 1 to obtain a first premix;
2) adding the first premix into a double-screw extruder from a main feeding port of the double-screw extruder and adding alkali-free glass fibers into the double-screw extruder from a side feeding port of the double-screw extruder respectively to obtain a second premix, wherein the length-diameter ratio of a screw of the double-screw extruder is 1:40, the temperature of each zone is set from the feeding port to a die orifice to be 80 ℃, 220 ℃, 250 ℃, 270 ℃, 280 ℃, 275 ℃ and 270 ℃, the temperature of the die orifice is 270 ℃, kneading the first premix in the double-screw extruder (manufactured by Nanjing Kogyo chemical engineering plant complete set Co., Ltd., type SK-40) at the rotating speed of 480rpm to obtain a melt-kneaded mixture, and the time of melt-kneading is 4 minutes;
3) the melt-kneaded material was extruded from a nozzle of a melt kneader into strands, the strands were cooled to a temperature not higher than the melting point of bio-based PA56 using water as a cooling medium, the cooled strands were cut in a pelletizer to obtain a flame-retardant bio-based PA56 composite material, and then the mechanical properties and combustion properties of the flame-retardant bio-based PA56 composite material were measured, and the measurement results are shown in table 2.
The twin-screw extruder is one of melt kneaders, and kneading in the twin-screw extruder is a kneading process.
Table 1 addition ratio table
Figure BDA0001552120670000041
TABLE 2 Performance results Table
Figure BDA0001552120670000042
Figure BDA0001552120670000051
As shown in Table 2, compared with the comparative examples, the long-chain bio-based PA510 and the MAH-g-POE elastomer play a synergistic role in improving the Comparative Tracking Index (CTI) and the Glow Wire Ignition Temperature (GWIT) of the flame-retardant bio-based PA56 composite material.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (7)

1. A flame-retardant bio-based PA56 composite material, characterized in that: the flame-retardant bio-based PA56 composite material comprises:
Figure FDA0003077178920000011
the compatibilizer is MAH-g-POE;
the flame retardant comprises brominated polystyrene.
2. The flame retardant bio-based PA56 composite material of claim 1, wherein: the relative viscosity of the bio-based PA56 is 2.0-4.0.
3. The flame retardant bio-based PA56 composite material of claim 1, wherein: the relative viscosity of the long-chain bio-based PA510 is 2.0-4.0.
4. The flame retardant bio-based PA56 composite material of claim 1, wherein: the flame retardant synergist comprises antimony trioxide.
5. The flame retardant bio-based PA56 composite material of claim 1, wherein: the reinforcing agent comprises alkali-free glass fibers.
6. The flame retardant bio-based PA56 composite material of claim 1, wherein: the flame-retardant bio-based PA56 composite material further comprises other processing aids;
the other processing aids are selected from any one or more of antioxidants, lubricants and dispersants.
7. A process for preparing a flame retardant bio-based PA56 composite according to any of claims 1-6, wherein: the method comprises the following steps:
1) premixing at least raw material components of a bio-based PA56, a long-chain bio-based PA510, a compatibilizer, a flame retardant and a flame retardant synergist to obtain a first premix;
2) adding the first premix into a double-screw extruder from a main feeding port of the double-screw extruder and adding the reinforcing agent into the double-screw extruder from a side feeding port of the double-screw extruder respectively to obtain a second premix, wherein the length-diameter ratio of a screw of the double-screw extruder is 1:40, the rotating speed of the screw is 200-500 rpm, the temperature of each area of the double-screw extruder is set to be 80 +/-10 ℃, 220 +/-15 ℃, 250 +/-5 ℃, 270 +/-10 ℃, 280 +/-5 ℃, 280 +/-10 ℃ and 275 +/-15 ℃ from the feeding port to a die orifice in sequence, and the temperature of the die orifice is 270 +/-10 ℃;
3) adding the second premix into a melt mixing machine for melt mixing, wherein the melt mixing temperature is 30-50 ℃ higher than the melting point of the bio-based PA56, and the melt mixing time is 0.25-5 minutes, so as to obtain a melt mixed material;
4) and extruding the molten and mixed material from a nozzle of a molten and mixed machine to obtain a strand material, wherein the temperature of the strand material is 230-350 ℃, then cooling the strand material in water, and cutting the cooled strand material in a granulator to obtain the flame-retardant bio-based PA56 composite material.
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