CN102492295B - Preparation method of ultrafine low precipitation red phosphorus inflaming retarding glass fiber reinforced nylon - Google Patents
Preparation method of ultrafine low precipitation red phosphorus inflaming retarding glass fiber reinforced nylon Download PDFInfo
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- B29C2948/92885—Screw or gear
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- B29C2948/92895—Barrel or housing
Abstract
The invention relates to a preparation method of an ultrafine low precipitation red phosphorus inflaming retarding glass fiber reinforced nylon. Raw materials comprise the following substances, by weight: 40-60% of nylon, 10-30% of ultrafine red phosphorus masterbatch, 5-15% of synergistic flame retardant, 5-30% of glass fiber and 1-5% of other auxiliaries. The ultrafine red phosphorus masterbatch is prepared by carrying out liquid nitrogen cryogenic grinding on red phosphorus to have a fineness higher than 1250 mesh; and carrying out melt blending on the red phosphorus, high temperature silicone oil and flexibilizer. The ultrafine low precipitation red phosphorus inflaming retarding glass fiber reinforced nylon is prepared by steps of: weighing the raw materials according to weight percentage; mixing well the raw materials in a high speed mixer; carrying out melt blending in a twin-screw extruder and adding the glass fiber simultaneously; and extruding for granulation. Technological conditions of the extruder are as below: a 1-2 zone temperature of the twin-screw extruder being 230-250 DEG C, a 3-4 zone temperature of 250-270 DEG C, a 5-6 zone temperature of 260-280 DEG C, a 7-8 zone temperature of 240-270 DEG C, a handpiece temperature of 230-250 DEG C and a screw revolving speed of 150-350 round / min.
Description
Technical field
The present invention relates to a kind of preparation method of ultrafine low precipitation red phosphorus inflaming retarding glass fiber reinforced nylon, can be applicable to the fields such as electronic apparatus, automobile engineering, belong to technical field of polymer materials.
Background technology
Red phosphorus flame-retardant glass fiber reinforced nylon material mechanical property is high, good electrical property, and low cigarette, low toxicity when burning, can not bring secondary harm to fire fighting, do not contain the objectionable impuritiess such as halogen, lead, cadmium, mercury, sexavalent chrome in addition, meet the RoHS of European Union environmental requirement, be widely used.But red phosphorus is under high temperature, high wet condition, especially easily be oxidized to phosphoric acid, again with material in some inorganic minerals generation phosphoric acid salt that reacts, these acid and salt be easy to from the polymer materials system to surface transport, the phenomenon that occur emitting acid, plays bloom, gently affect outward appearance, open circuit, equipment can not use, and is heavy cause that electrical equipment punctures, short circuit, cause that whole equipment damages and even cause fire.
At present, a main method that solves problems is micro encapsulation to be carried out on the red phosphorus surface process, isolated moisture, air, the stability of increase red phosphorus.As patents such as Chinese patent CN1238793N, CN1775664A, CN1632057A, CN8814159A, process by the coating to the red phosphorus powder, stablized the performance of red phosphorus.But this stable red phosphorus is in nylon and glass fibre reinforced composite material, and under high temperature, strong shearing action, the capsule layer of red phosphorus is destroyed or partial destruction inevitably, still can deterioration failure.
Chinese patent CN101503568B has introduced organic and inorganic compound coating, thermoset coating and thermoplastic covering and use when processing red phosphorus, make coating layer when production is extruded, and plays lubrication, has avoided as far as possible the destruction of coating layer.Chinese patent CN101684196A uses ammonium sulfate as initiator, prepares the micro encapsulation red phosphorus that point of ignition surpasses 450 ℃, and with modified layered pair of Ripon powder as synergistic flame retardant.
Another method that solution red phosphorus is separated out Problem of Failure is to add acid absorber or unicorn to separate out stablizer in matrix material, and the phosphorus substance of separating out is on a small quantity neutralized.Adopted exactly examples of such additives as Chinese patent CN101619166B and CN102115595A, to reduce separating out of red phosphorus.
Above patent documentation all the size of not mentioned red phosphorus powder for the impact of separating out.The particle diameter of micro encapsulation red phosphorus powder in the market is generally the 100-800 order.
Summary of the invention
The present invention proposes the low preparation method of red phosphorus glass fiber enhanced nylon that separates out of a kind of super-refinement.The method is pulverized the method for red phosphorus by liquid nitrogen freezing, make more than the red phosphorus particle diameter refine to 1250 orders, is reduced under high temperature, strong shearing action the destruction to red phosphorus.Utilize simultaneously high-temperature silicon oil and toughner double-coated red phosphorus surface, play the effect of protection red phosphorus and increase red phosphorus consistency.
The present invention adopts following technical scheme:
After nylon, super-refinement red phosphorus master batch, synergistic flame retardant, other auxiliary agents were mixed, melt blending in twin screw extruder, added glass fibre, extruding pelletization simultaneously; The forcing machine processing condition are: twin screw extruder 1-2 district temperature is 230-250 ℃, 3-4 district temperature is 250-270 ℃, and 5-6 district temperature is 260-280 ℃, and 7-8 district temperature is 240-270 ℃, head temperature is 230-250 ℃, and screw speed is 150-350 rev/min;
Above-mentioned each raw material consumption by weight percentage is as follows:
Nylon 40～60%,
Super-refinement red phosphorus master batch 10～30%,
Synergistic flame retardant 5～15%,
Glass fibre 5～30%
Other auxiliary agents 1～5%
Above-mentioned super-refinement red phosphorus master batch preparation process is:
1) red phosphorus is pulverized 1250 order calibration sieves through liquid nitrogen freezing, obtained the super-refinement red phosphorus of particle diameter more than 1250 orders;
2) super-refinement red phosphorus and high-temperature silicon oil are uniformly mixed, the consumption of aforementioned high-temperature silicon oil is 1～5% of super-refinement red phosphorus weight;
3) will be through step 2) super-refinement red phosphorus and the toughner blend granulation on forcing machine processed, the consumption of toughner is 30～70% of super-refinement red phosphorus master batch weight, the forcing machine processing condition are: twin screw extruder 1-2 district temperature is 160-190 ℃, 3-4 district temperature is 200-220 ℃, 5-6 district temperature is 210-230 ℃, 7-8 district temperature is 210-230 ℃, and head temperature is 170-190 ℃, and screw speed is 150-300 rev/min.
Above-mentioned nylon is the mixture of nylon 66, nylon 6 or both arbitrary proportions, and viscosity is at 2.4-2.7.
Above-mentioned synergistic flame retardant is magnesium hydroxide or aluminium-hydroxide powder, and fineness is 400～800 orders, is beneficial to disperse;
Above-mentioned alkali-free continuous glass fibre, filament diameter, at 8～18 μ m, to keep intensity, and are beneficial to smooth surface;
Above-mentioned red phosphorus is commercially available, and its particle diameter is usually at the 100-800 order,
Why the particle diameter of above-mentioned ultra-fine red phosphorus requires more than 1250 orders, is in order to be reduced under high temperature, strong shearing action the destruction to red phosphorus in subsequent handling.
Above-mentioned high-temperature silicon oil is preferably boiling point at the silicone oil more than 400 ℃, to guarantee that when the high temperature process, silicone oil is non-volatile, plays the protection lubrication.
Above-mentioned toughner is SBS or SEBS through maleic anhydride, glycidyl acrylate graft modification, melting index is 0.5-10g/10min, percentage of grafting is 0.3%-1.5%, its reason is that the applicant finds after deliberation, if melting index not in the 0.5-10g/10min scope, can cause processing difficulties; And percentage of grafting is in the 0.3%-1.5% scope, and toughening effect is best, and too low toughening effect is not obvious, and too high material has obvious irritating smell.
Other above-mentioned auxiliary agents are conventional oxidation inhibitor and lubricant, and both concrete consumptions do not have special requirement, and its total amount control gets final product 11～5%.Preferred 1010,168 mixtures in 1: 1 ratio of oxidation inhibitor wherein, lubricant preferably selects calcium stearate, Zinic stearas, EBS or polyethylene wax.
The ultrafine low precipitation red phosphorus inflaming retarding glass fiber reinforced nylon that employing the present invention makes is when having guaranteed material mechanical performance and flame retardant resistance, and the phosphorus amount of separating out is minimum is 25ppm, can match in excellence or beauty with the phosphorus amount of separating out of German BASF like product.
Specific embodiments
Following examples are in order to further explanation the present invention, but the present invention is not only limited to these embodiment.
One, the preparation of super-refinement red phosphorus master batch
The red phosphorus of particle diameter more than 1250 orders of pulverizing through liquid nitrogen mixes with 1% high-temperature silicon oil, then with maleic anhydride graft SBS extruding pelletization in forcing machine, in master batch, toughner content is 70%, is super-refinement red phosphorus master batch A.
The red phosphorus of particle diameter more than 1250 orders of pulverizing through liquid nitrogen mixes with 3% high-temperature silicon oil, then with maleic anhydride graft SEBS extruding pelletization in forcing machine, in master batch, toughner content is 50%, is super-refinement red phosphorus mother particle B.
The red phosphorus of particle diameter more than 1250 orders of pulverizing through liquid nitrogen mixes with 5% high-temperature silicon oil, then with glycidyl acrylate SBS extruding pelletization in forcing machine, in master batch, toughner content is 30%, is super-refinement red phosphorus master batch C.
The red phosphorus of particle diameter more than 1250 orders of pulverizing through liquid nitrogen mixes with 5% high-temperature silicon oil, then with glycidyl acrylate SEBS extruding pelletization in forcing machine, in master batch, toughner content is 30%, is super-refinement red phosphorus master batch D.
Two, each component is mixed in high-speed mixer by listed formula ratio in table 1, melt blending in twin screw extruder, add glass fibre, extruding pelletization simultaneously.The forcing machine processing condition are: twin screw extruder 1-2 district temperature is 230-250 ℃, 3-4 district temperature is 250-270 ℃, and 5-6 district temperature is 260-280 ℃, and 7-8 district temperature is 240-270 ℃, head temperature is 230-250 ℃, and screw speed is 150-350 rev/min.
Resulting materials, 110 ℃ of dryings 4 hours, makes batten through injection moulding, presses ISO and UL standard testing performance, the results are shown in Table 2.
Embodiment 1,2,3,4 and Comparative Examples 1,2 the formula (table 1)
Embodiment 1,2,3,4 and Comparative Examples 1,2 performance synopsis (table 2)
| Test event | Comparative Examples 1 | Comparative Examples 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Tensile strength (MPa) | 101 | 115 | 70 | 97 | 128 | 120 |
| Flexural strength (MPa) | 142 | 159 | 91 | 136 | 172 | 155 |
| Modulus in flexure (MPa) | 5223 | 6028 | 3964 | 4902 | 8013 | 6207 |
| Notched Izod impact strength (KJ/m 2) | 6.2 | 7.7 | 12.6 | 11.9 | 9.5 | 9.1 |
| Flame retardant resistance (3.2mm) | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| The phosphorus amount of separating out (ppm) | 1025 | 886 | 75 | 122 | 96 | 25 |
Claims (1)
1. the preparation method of a ultrafine low precipitation red phosphorus inflaming retarding glass fiber reinforced nylon, is characterized in that
After nylon, super-refinement red phosphorus master batch, synergistic flame retardant, other auxiliary agents were mixed, melt blending in twin screw extruder, added glass fibre, extruding pelletization simultaneously; The forcing machine processing condition are: twin screw extruder 1-2 district temperature is 230-250 ℃, 3-4 district temperature is 250-270 ℃, and 5-6 district temperature is 260-280 ℃, and 7-8 district temperature is 240-270 ℃, head temperature is 230-250 ℃, and screw speed is 150-350 rev/min;
Above-mentioned each raw material consumption by weight percentage is as follows:
Above-mentioned super-refinement red phosphorus master batch preparation process is:
1) red phosphorus is pulverized 1250 order calibration sieves through liquid nitrogen freezing, obtained the super-refinement red phosphorus of particle diameter more than 1250 orders;
2) super-refinement red phosphorus and high-temperature silicon oil are uniformly mixed, the consumption of aforementioned high-temperature silicon oil is 1～5% of super-refinement red phosphorus weight;
3) will be through step 2) super-refinement red phosphorus and the toughner blend granulation on forcing machine processed, the consumption of toughner is 30～70% of super-refinement red phosphorus master batch weight, the forcing machine processing condition are: twin screw extruder 1-2 district temperature is 160-190 ℃, 3-4 district temperature is 200-220 ℃, 5-6 district temperature is 210-230 ℃, 7-8 district temperature is 210-230 ℃, and head temperature is 170-190 ℃, and screw speed is 150-300 rev/min;
Described nylon is the mixture of nylon 66, nylon 6 or both arbitrary proportions, and viscosity is at 2.4-2.7;
Described synergistic flame retardant is magnesium hydroxide or aluminium-hydroxide powder, and granularity is 400～800 orders;
Described glass fibre is the alkali-free continuous glass fibre, and filament diameter is at 8～18 μ m;
The particle diameter of described red phosphorus is at the 100-800 order;
Described high-temperature silicon oil is that boiling point is at the silicone oil more than 400 ℃;
Described toughner is SBS or SEBS through maleic anhydride, glycidyl acrylate graft modification, and melting index is 0.5-10g/10min, and percentage of grafting is 0.3%-1.5%;
Described other auxiliary agents are the mixture of oxidation inhibitor, lubricant.
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