CN107418201B - Efficient halogen-free flame-retardant reinforced nylon composite material and preparation method thereof - Google Patents

Efficient halogen-free flame-retardant reinforced nylon composite material and preparation method thereof Download PDF

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CN107418201B
CN107418201B CN201710764615.5A CN201710764615A CN107418201B CN 107418201 B CN107418201 B CN 107418201B CN 201710764615 A CN201710764615 A CN 201710764615A CN 107418201 B CN107418201 B CN 107418201B
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刘典典
冉进成
陈捷豪
官炳荣
官炳桂
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Guangdong Huaju Technology Co ltd
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    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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Abstract

The invention discloses a high-efficiency halogen-free flame-retardant reinforced nylon composite material which comprises the following components in parts by weight: 41.1 to 71.1 percent of nylon resin; 7.5 to 15 percent of flame retardant diethyl hypophosphite; 3-7.5% of flame retardant melamine polyphosphate; 0.6 to 5 percent of modified synergistic flame retardant; 10-40% of alkali-free chopped glass fiber; 1-1.4 of other auxiliary agents; the modified synergistic flame retardant is one or more mixture particles of zinc borate, boehmite, vermiculite and mica. The invention also provides a method for preparing the composite material. The surface modification is carried out on the synergistic flame retardant, so that the synergistic flame retardant effect of the synergistic flame retardant is greatly improved, the processing performance of the material is improved, the mechanical performance of the base material is not influenced, and the use range of the material is enlarged; the invention utilizes the synergistic flame-retardant effect of the flame-retardant synergist, greatly reduces the addition of the main flame retardant diethyl hypophosphite, improves the flame-retardant property, improves the mechanical property and the processing property, and greatly reduces the overall material cost.

Description

Efficient halogen-free flame-retardant reinforced nylon composite material and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-efficiency halogen-free flame-retardant reinforced nylon composite material and a preparation method thereof.
Background
With the rapid development of economy in China, the application of engineering plastics in the electronic and electrical industry is rapidly increased, wherein nylon (PA) is the most widely applied. The glass fiber reinforced nylon has excellent mechanical property and heat resistance, but the flame retardant property of the glass fiber reinforced nylon cannot meet the requirements of the electronic and electrical industry. The flame retardant is added in a large amount, so that although the flame retardant property of the material is improved to a certain extent, the mechanical property, the electrical insulation property and the like of the material are greatly influenced, and the application of the material in the electronic and electrical industry is directly influenced.
In addition, with the improvement of environmental protection requirements, the traditional brominated flame retardant can not meet the requirements of Rohs and WEEE instructions of European Union, the halogen-free flame retardant is highly regarded, the common halogen-free flame retardant has inorganic filler for flame retarding, but the use is limited because the flame retarding effect can be achieved only by adding too high parts; the red phosphorus flame retardant is forbidden in many countries due to potential safety hazards caused by precipitation in the using process; also, phosphorus-nitrogen flame retardants, most commonly Exolit OP1314 from Clarian chemical Limited, are very expensive and cause a dramatic rise in downstream costs.
Disclosure of Invention
The invention aims to provide an efficient halogen-free flame-retardant reinforced nylon composite material and a preparation method thereof, wherein the efficient halogen-free flame-retardant reinforced nylon composite material has excellent flame-retardant performance, low cost, good mechanical properties and processability, and can be applied to preparation of electronic and electric parts with high requirements.
In order to solve the technical problems, the invention provides a high-efficiency halogen-free flame-retardant reinforced nylon composite material which comprises the following components in parts by weight:
Figure BDA0001393847870000011
the modified synergistic flame retardant is one or more mixture particles of zinc borate, boehmite, vermiculite and mica;
the modification method of the modified synergistic flame retardant comprises the following steps: reacting the flame-retardant synergist with diisocyanate to prepare isocyanate activated particles; adding 100 parts by mass of flame-retardant synergist particles at 100 ℃ by using anhydrous toluene as a dispersing agent, dripping 12-15 parts of isocyanate under stirring, and removing a solvent by using a rotary evaporator after 60min to obtain isocyanate modified particles; adding the isocyanate modified particles into 1 percent of titanate solution according to the weight percentage, and stirring at high speed to obtain the final modified flame-retardant synergist.
Preferably, the paint comprises the following components in parts by weight:
Figure BDA0001393847870000021
preferably, the paint comprises the following components in parts by weight:
Figure BDA0001393847870000022
preferably, the nylon resin is one or a mixture of more of PA6, PA66, PA1212 and PA 612.
Preferably, the alkali-free chopped glass fiber has a diameter of 9-13 microns and a length of 3-5 mm.
The invention also provides a method for preparing the high-efficiency halogen-free flame-retardant reinforced nylon composite material, which comprises the following steps:
weighing various raw materials according to the weight fraction ratio, and drying the nylon resin at 90-110 ℃ for 8-12 h;
step two, reacting the flame-retardant synergist with diisocyanate to prepare isocyanate activated particles: adding 100 parts by mass of flame-retardant synergist particles at 100 ℃ by using anhydrous toluene as a dispersing agent, dripping 12-15 parts of isocyanate under stirring, and removing a solvent by using a rotary evaporator after 60min to obtain isocyanate modified particles; adding the isocyanate modified particles into 1 percent of titanate solution according to the weight percentage, and stirring at a high speed for 2min to obtain the final modified flame-retardant synergist. (ii) a
Thirdly, placing the dried raw materials such as the nylon resin, the main flame retardant, the modified flame-retardant synergist and the like into a high-speed mixer, and stirring for 3-5 min to uniformly mix the raw materials;
and step four, adding the uniformly mixed raw materials into a hopper of a double-screw extruder, adding the alkali-free chopped glass fibers from a feeding port at the middle section side of the extruder, and extruding and granulating to prepare the halogen-free flame-retardant reinforced nylon composite particles for injection molding.
The technical scheme of the invention has the following beneficial effects:
(1) the invention carries out surface modification on the flame-retardant synergist, not only can greatly improve the synergistic flame-retardant effect of the synergistic flame retardant, but also improves the processing performance of the material, does not influence the mechanical performance of the base material, and enlarges the application range of the material.
(2) The invention utilizes the synergistic flame-retardant effect of the flame-retardant synergist to greatly reduce the addition of the main flame retardant diethyl hypophosphite, and simultaneously, the flame-retardant property is improved, and the mechanical property and the processing property are improved, so that the overall material cost can be greatly reduced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to specific embodiments.
The invention also provides a method for preparing the high-efficiency halogen-free flame-retardant reinforced nylon composite material, which comprises the following steps:
weighing various raw materials according to the weight fraction ratio, and drying the nylon resin at 90-110 ℃ for 8-12 h;
step two, reacting the flame-retardant synergist with diisocyanate to prepare isocyanate activated particles: adding 100 parts by mass of flame-retardant synergist particles at 100 ℃ by using anhydrous toluene as a dispersing agent, dripping 12-15 parts of isocyanate under stirring, and removing a solvent by using a rotary evaporator after 60min to obtain isocyanate modified particles; adding isocyanate modified particles into 1% titanate solution according to the weight percentage ratio, and stirring at a high speed for 2min to obtain the final modified flame-retardant synergist; isocyanate can form a layer of isocyanate active molecular film on the surface of the flame-retardant synergist, so that the surface of the flame-retardant synergist is provided with active groups, and then titanate is attached to the surface of the flame-retardant synergist, so that on one hand, the compatibility of the flame-retardant synergist and matrix resin can be improved, and meanwhile, a certain titanate solvent plays a role in promoting flame retardance and improves flame retardance.
Thirdly, placing the dried raw materials such as the nylon resin, the main flame retardant, the modified flame-retardant synergist and the like into a high-speed mixer, and stirring for 3-5 min to uniformly mix the raw materials;
and step four, adding the uniformly mixed raw materials into a hopper of a double-screw extruder, adding the alkali-free chopped glass fibers from a feeding port at the middle section side of the extruder, and extruding and granulating to prepare the halogen-free flame-retardant reinforced nylon composite particles for injection molding.
Specifically, in this example, the nylon 66 resin was first dried at 100 ℃ for 8 hours before use. Placing the dried nylon resin, the main flame retardant, the modified flame-retardant synergist and other raw materials into a high-speed mixer, and stirring for 3-5 min to uniformly mix the raw materials; adding into a double-screw extruder, and adding chopped glass fiber at a lateral feeding port. The processing technology is as follows: the temperature of the first zone is 250-260 ℃, the temperature of the second zone is 265-280 ℃, the temperature of the third zone is 265-280 ℃, the temperature of the fourth zone is 265-280 ℃, the temperature of the fifth zone is 260-275 ℃, the temperature of the sixth zone is 250-265 ℃, the temperature of the seventh zone is 240-260 ℃, the temperature of the eighth zone is 240-260 ℃, the temperature of the ninth zone is 240-265 ℃ and the rotating speed of the main engine is 240-400 r/min. And cooling, drying and granulating after extrusion to obtain the reinforced nylon composite material.
According to the preparation method, the weight percentage formula is shown in the table 1:
TABLE 1 component contents of examples 1-6 and comparative examples
Figure BDA0001393847870000041
The performance detection method comprises the following steps:
tensile Strength test was conducted according to ASTM-D638, specimen type I, specimen size (mm): (165. + -.2) × (12.70. + -. 0.2) × (3.20. + -. 0.2), and the drawing speed was 50 mm/min.
Flexural strength and flexural modulus were examined according to ASTM-D790, specimen size (mm): (127. + -. 2) × (12.7. + -. 0.2) × (3.20. + -. 0.2), and the bending speed was 13 mm/min.
Notched impact strength was tested according to ASTM-D256, and the specimen type was V notch type, specimen size (mm): 63.5 × (12.7 ± 0.2) × (3.2 ± 0.2); the notch type is V-notch type, and the residual thickness of the notch is 10.16 mm.
The flame retardant property is injection molded into standard combustion test bars according to the US UL standard.
TABLE 2 high-efficiency halogen-free flame-retardant reinforced nylon composite material
Figure BDA0001393847870000042
Figure BDA0001393847870000051
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (4)

1. The efficient halogen-free flame-retardant reinforced nylon composite material is characterized by comprising the following components in parts by weight:
41.1 percent of nylon resin
Flame retardant diethyl hypophosphite 7.5%
Flame retardant melamine polyphosphate 5%
5 percent of modified synergistic flame retardant
40 percent of alkali-free chopped glass fiber
0.3 percent of antioxidant
0.8 percent of lubricant
KH-550 0.3%;
The synergistic flame retardant is one or mixture particles of boehmite and mica;
the modification method of the modified synergistic flame retardant comprises the following steps: reacting the synergistic flame retardant with diisocyanate to prepare isocyanate activated particles; adding 100 parts by mass of synergistic flame retardant particles at 100 ℃ by using anhydrous toluene as a dispersing agent, dripping 12-15 parts of isocyanate under stirring, and removing the solvent by using a rotary evaporator after 60min to obtain isocyanate modified particles; adding the isocyanate modified particles into 1 percent of titanate solution according to the weight percentage, and stirring at high speed to obtain the final modified synergistic flame retardant.
2. The efficient halogen-free flame-retardant reinforced nylon composite material as claimed in claim 1, wherein: the nylon resin is one or a mixture of PA6, PA66, PA1212 and PA 612.
3. The efficient halogen-free flame-retardant reinforced nylon composite material as claimed in any one of claims 1-2, wherein: the diameter of the alkali-free chopped glass fiber is 9-13 microns, and the length of the alkali-free chopped glass fiber is 3-5 mm.
4. The preparation method of the high-efficiency halogen-free flame-retardant reinforced nylon composite material as claimed in any one of claims 1 to 3 is characterized by comprising the following steps:
weighing various raw materials according to the weight fraction ratio, and drying the nylon resin at 90-110 ℃ for 8-12 h;
step two, reacting the synergistic flame retardant with diisocyanate to prepare isocyanate activated particles: adding 100 parts by mass of flame-retardant synergist particles at 100 ℃ by using anhydrous toluene as a dispersing agent, dripping 12-15 parts of isocyanate under stirring, and removing the solvent by using a rotary evaporator after 60min to obtain isocyanate modified particles; adding isocyanate modified particles into 1% titanate solution according to the weight percentage ratio, and stirring at a high speed for 2min to obtain the final modified synergistic flame retardant;
thirdly, placing the dried nylon resin, the flame retardant diethyl hypophosphite, the flame retardant melamine polyphosphate, the modified synergistic flame retardant, the antioxidant, the lubricant and the KH-550 raw materials into a high-speed mixer, and stirring for 3-5 min to uniformly mix the raw materials;
and step four, adding the uniformly mixed raw materials into a hopper of a double-screw extruder, adding the alkali-free chopped glass fibers from a feeding port at the middle section side of the extruder, and extruding and granulating to prepare the halogen-free flame-retardant reinforced nylon composite particles for injection molding.
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CN111040245B (en) * 2019-12-18 2022-05-31 江苏集萃先进高分子材料研究所有限公司 Pyropolyphosphoric acid imidazole flame retardant and preparation method thereof
CN112029280B (en) * 2020-11-06 2021-04-02 江苏金发科技新材料有限公司 Halogen-free flame-retardant polyamide composite material and preparation method thereof
CN115304913B (en) * 2022-08-24 2023-07-18 横店集团得邦工程塑料有限公司 Reinforced flame-retardant hypophosphite/nylon composite material with high glow wire ignition temperature and preparation method thereof
CN116515285A (en) * 2023-05-18 2023-08-01 徐州腾飞工程塑料有限公司 Low-cost halogen-free flame-retardant glass fiber reinforced PA6 material and preparation method thereof

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