CN113956655A - Glass fiber reinforced flame-retardant PA66 material and preparation method thereof - Google Patents
Glass fiber reinforced flame-retardant PA66 material and preparation method thereof Download PDFInfo
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Abstract
The application relates to the field of nylon materials, in particular to a glass fiber reinforced flame-retardant PA66 material and a preparation method thereof. The glass fiber reinforced flame-retardant PA66 material comprises the following components in percentage by weight: PA 6654-66%, glass fiber 13-20%, flame-retardant master batch 14-16%, POE-g-MAH 4-6%, and black master batch 3-4%. According to the application, the glass fiber is compounded with the flame-retardant master batch, the POE-g-MAH and the black master batch, the raw materials are uniformly mixed and then extruded out through the screw extruder for granulation, the operation is simple, and the prepared glass fiber reinforced flame-retardant PA66 material has good flame retardant property and low temperature resistance, and is convenient to popularize and use.
Description
Technical Field
The application relates to the field of nylon materials, in particular to a glass fiber reinforced flame-retardant PA66 material and a preparation method thereof.
Background
The glass fiber reinforced PA66 material is one of modified polyamides, has excellent wear resistance and self-lubricating property and higher mechanical strength, and is widely applied to the preparation of automobile industry, instrument shells and other products requiring impact resistance and high strength.
In the prior art, the UL94 flame retardant grade of the glass fiber reinforced PA66 material is V2 grade, in order to improve the flame retardant property of the glass fiber reinforced PA66 material, phosphorus flame retardants, nitrogen flame retardants, bromine flame retardants and the like are usually added into the glass fiber reinforced PA66, and the UL94 flame retardant grade of the prepared glass fiber reinforced flame retardant PA66 material can reach V0 grade.
However, most of the existing flame retardants are low molecules, the compatibility with PA66 is poor, and the glass fiber reinforced flame retardant PA66 material added with the flame retardant has poor low-temperature resistance, so that the flame retardant is difficult to be well applied to a low-temperature environment.
Disclosure of Invention
In order to improve the low temperature resistance of the glass fiber reinforced flame retardant PA66 material, the application provides a glass fiber reinforced flame retardant PA66 material and a preparation method thereof.
In a first aspect, the application provides a glass fiber reinforced flame retardant PA66 material, which adopts the following technical scheme:
the glass fiber reinforced flame-retardant PA66 material comprises the following components in percentage by weight: PA 6654-66%, glass fiber 13-20%, flame-retardant master batch 14-16%, POE-g-MAH 4-6%, and black master batch 3-4%.
By adopting the technical scheme, the flame retardant performance of the PA66 is improved by using the flame retardant master batch, and the flame retardant master batch has better compatibility with PA66 compared with a flame retardant and can be uniformly dispersed in PA 66; on the basis, the components of the flame-retardant PA 3978 glass fiber reinforced flame-retardant PA66 glass fiber reinforced flame-retardant PA 94 material are also matched with POE-g-MAH, so that the compatibility of the flame-retardant master batch and PA66 can be further improved, the fluidity of PA66 can be improved, and the glass fiber can be uniformly dispersed, the UL94 flame-retardant grade of the prepared glass fiber reinforced flame-retardant PA66 glass fiber reinforced flame-retardant PA66 material can reach V0 grade, and the glass fiber reinforced flame-retardant PA66 glass fiber reinforced flame-retardant PA 94 glass fiber reinforced flame-retardant PA66 glass fiber reinforced flame-retardant PA 40 glass fiber reinforced flame-retardant material has particularly good structural strength at-40 ℃ and excellent low-temperature resistance; in addition, the black master batch in the formula can color the glass fiber reinforced flame-retardant PA66 material on one hand, and the carbon black can reinforce the material on the other hand, so that the situation that the hardness of the material is reduced due to the addition of POE-g-MAH is reduced, and the glass fiber reinforced flame-retardant PA66 material is ensured to have good comprehensive performance.
Preferably, the flame-retardant master batch is prepared by extruding and granulating the following raw materials in percentage by weight: 60-70% of flame retardant, 25-30% of POE elastomer, 2-5% of silane coupling agent and 3-5% of antioxidant.
Through adopting above-mentioned technical scheme, in the fire-retardant master batch, the fire retardant is fire-retardant substrate, POE elastomer is as the shaping substrate, utilize the good processing property of POE elastomer to wrap up the fire retardant, wherein silane coupling agent can further promote the fire retardant to disperse in POE better, the antioxidant then can effectively improve the oxidation resistance of fire retardant, it has better mobility for single fire retardant to make fire-retardant master batch from this, be convenient for transportation and storage, when it can effectively improve PA66 fire resistance, can also reduce the influence of fire retardant to PA66 low temperature resistant performance, make glass fibre reinforcing fire-retardant PA66 material have excellent low temperature resistant performance.
Preferably, the flame retardant is a red phosphorus flame retardant.
By adopting the technical scheme, the red phosphorus flame retardant is a flame retardant represented by red phosphorus and has the characteristics of excellent high temperature resistance, no volatilization and the like. In the phosphorus flame retardant, the flame retardant effect of red phosphorus is finally high, probably because the red phosphorus is a complete phosphorus simple substance in theory, the flame retardant mechanism of the red phosphorus in resin is that phosphoric acid is formed to be used as a dehydrating agent and promoted to be carbon, and the heat conduction from flame to a condensed phase is reduced due to the generation of the carbon. However, the compatibility of red phosphorus with resin is poor, red phosphorus is easy to be changed into phosphoric acid when being exposed in plastic in a high-temperature and high-humidity environment for a long time, the two ends of the plastic are tightly attached to metal conductors with voltage difference, and the phosphoric acid can cause metal atoms to be dissociated into metal ions which are dissolved in the phosphoric acid. The insulating plastic intermediate the metallic conductors at both ends becomes conductive plastic, thus creating electrical insulation quality/safety issues.
However, the flame-retardant master batch prepared from the red phosphorus flame retardant has good insulation in a high-temperature and high-humidity environment, probably because the red phosphorus is wrapped by the POE, the POE has excellent electrical insulation, and in addition, the flame-retardant master batch has good performances of aging resistance, ozone resistance, chemical medium resistance and the like, and is matched with an antioxidant, so that the system of the flame-retardant master batch has good electrochemical stability.
Preferably, the preparation method of the red phosphorus flame retardant comprises the following steps:
adding red phosphorus and a dispersing agent into water, stirring until the red phosphorus is uniformly dispersed to obtain a red phosphorus dispersion liquid, adding aluminum sulfate into the red phosphorus dispersion liquid, wherein the mass ratio of the aluminum sulfate to the red phosphorus is (3-4): 1, heating to 50 +/-2 ℃, keeping the temperature, standing for 8-10min, then continuously heating to 65 +/-2 ℃, slowly dripping a sodium carbonate solution while stirring, adjusting the pH to 5-6, keeping the temperature, reacting for 2h, cooling, filtering, washing and drying the obtained product to obtain the red phosphorus flame retardant.
Through adopting above-mentioned technical scheme, the red phosphorus flame retardant of this application carries out surface treatment with aluminum sulfate for the red phosphorus surface cladding has aluminium hydroxide, it can reduce red phosphorus flame retardant oxidation and become phosphoric acid, reduce the moisture absorption rate of red phosphorus simultaneously, improve the stability of red phosphorus flame retardant, wherein heat to 50 ℃ in the reaction process and keep warm and stew for 8-10min, the red phosphorus flame retardant stability of making from this is more excellent, this probably because this stage aluminum sulfate evenly attaches to the red phosphorus surface steadily earlier, the sodium carbonate solution that drops afterwards reacts with aluminum sulfate and generates aluminium hydroxide cladding on the red phosphorus surface, form aluminium hydroxide encapsulation red phosphorus at last.
Preferably, the POE elastomer is one of Dow 8150, VM-6202 and DF-710.
By adopting the technical scheme, the Dow 8150, VM-6202 and DF-710 have particularly good processing flowability, and can be well extruded and granulated in the application, so that the preparation efficiency of the flame-retardant master batch is improved.
Preferably, the weight ratio of the glass fiber, the flame-retardant master batch and the POE-g-MAH is 3:3: 1.
By adopting the technical scheme, when the weight ratio of the glass fiber, the flame-retardant master batch and the POE-g-MAH is 3:3:1, the flame retardance and the low-temperature resistance of the prepared glass fiber reinforced flame-retardant PA66 material are obviously superior to those of other weight ratios, so that the glass fiber reinforced flame-retardant PA66 material is further preferred.
Preferably, the POE-g-MAH has a melt index of 1.5-2.0g/10min (190 ℃, 2.16 kg) and a grafted MAH content of 0.8-1.2%.
By adopting the technical scheme, the melt index and the grafting amount of the POE-g-MAH influence the performance of the POE-g-MAH to a certain extent, for example, the higher the melt index is, the more the grafting amount is, the lower the mechanical strength of the material is; when the melt index is lowered and the graft amount is reduced, the compatibility of each component in the material is difficult to be effectively improved, and it is difficult to obtain more excellent low-temperature resistance. The materials produced in the present application within the above-described parameter ranges are preferred because they have both good mechanical strength and low temperature resistance.
Preferably, the filament diameter of the glass fiber is 11-17 μm, the filament length is 10-350 μm, and the length-diameter ratio is (5-20): 1.
By adopting the technical scheme, when the existing short fibers or long fibers are added into nylon, the fibers are easy to float, the attractiveness of a product is influenced, and the effect of reinforcing the glass fibers cannot be expected. The glass fiber with small particle size is selected, so that the reinforcing effect on PA66 is good, the glass fiber can be effectively and well dispersed in PA66, and floating fiber is reduced.
Preferably, the content of carbon black in the black master batch is more than or equal to 40%.
By adopting the technical scheme, when the content of the carbon black is more than or equal to 40%, the reinforcing effect of the black master batch on PA66 can be effectively improved, so that the black master batch is preferred.
In a second aspect, the application provides a preparation method of a glass fiber reinforced flame retardant PA66 material, which adopts the following technical scheme:
a preparation method of a glass fiber reinforced flame-retardant PA66 material is used for preparing the glass fiber reinforced flame-retardant PA66 material, and comprises the following steps: weighing the components according to the set weight percentage, uniformly mixing the components, putting the mixture into a screw extruder, melting and extruding the mixture at the processing temperature of 230-260 ℃, granulating and drying to obtain the glass fiber reinforced flame retardant PA66 material.
Through adopting above-mentioned technical scheme, this application extrudes the granulation in passing through screw extruder after with the raw materials mixing, and its easy operation, the glass fiber reinforcement fire-retardant PA66 material that makes has good fire behavior and low temperature resistant performance, is convenient for be used widely.
In summary, the present application has the following beneficial effects:
1. according to the application, the glass fiber is compounded with the flame-retardant master batch, the POE-g-MAH and the black master batch, so that the prepared glass fiber reinforced flame-retardant PA66 material has good flame retardant property and low temperature resistance.
2. The application selects self-made red phosphorus flame retardant and POE elastomer and other auxiliaries to prepare for the fire-retardant master batch, and the fire-retardant master batch that it made has good chemical stability, increases the security of glass fiber reinforced fire-retardant PA66 material.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples.
1. Preparation of Red phosphorus flame retardant (aluminum hydroxide-coated)
1-1, Red phosphorus flame retardant-1
The preparation method of the red phosphorus flame retardant-1 comprises the following steps:
adding 18kg of red phosphorus powder (industrial grade, CAS number 7723-14-0) and 1kg of sodium dodecyl sulfate into 50L of water, and stirring until the red phosphorus is uniformly dispersed to obtain a red phosphorus dispersion liquid; adding aluminum sulfate octadecahydrate into the red phosphorus dispersion liquid, wherein the mass ratio of the aluminum sulfate octadecahydrate to the red phosphorus can be (3-4): 1, in the application, 27.74kg of the aluminum sulfate octadecahydrate is specifically added, heating is carried out to 50 ℃, then heat preservation and standing are carried out for 9min, the heating temperature can fluctuate within the range of +/-2 ℃, and the standing time can fluctuate within the range of 8-10 min; and continuously heating to 65 ℃, wherein the heating temperature can also fluctuate within the range of +/-2 ℃, then slowly dripping 10wt% of sodium carbonate aqueous solution, adjusting the pH value to 5.5, carrying out heat preservation reaction for 2 hours, drying the obtained product in an oven at 85 ℃ until the water content is less than or equal to 0.2% after cooling, suction filtration and washing, and grinding until the average particle size is 2 mu m to obtain the red phosphorus flame retardant-1.
1-2, red phosphorus flame retardant-2
The preparation method of the red phosphorus flame retardant-2 comprises the following steps:
adding 18kg of red phosphorus powder (industrial grade, CAS number 7723-14-0) and 1kg of sodium dodecyl sulfate into 50L of water, and stirring until the red phosphorus is uniformly dispersed to obtain a red phosphorus dispersion liquid; adding aluminum sulfate octadecahydrate into the red phosphorus dispersion liquid, wherein the mass ratio of the aluminum sulfate octadecahydrate to the red phosphorus can be (3-4): 1, specifically adding 27.74kg of the aluminum sulfate octadecahydrate into the dispersion liquid, heating to 65 ℃, wherein the heating temperature can also fluctuate within the range of +/-2 ℃, then slowly dripping 10wt% of sodium carbonate aqueous solution, adjusting the pH value to 5.5, carrying out heat preservation reaction for 2 hours, cooling, filtering and washing the obtained product, drying in an oven at 85 ℃ until the water content is less than or equal to 0.2%, and grinding until the average particle size is 2 mu m, thus obtaining the red phosphorus flame retardant-2.
2. Preparation example of flame-retardant Master batch
2-1, red phosphorus master batch a
The preparation method of the red phosphorus master batch a comprises the following steps:
taking 65kg of the red phosphorus flame retardant-1 prepared in the preparation example 1, adding 28kg of POE elastomer (with the trademark of Dow 8150), 4kg of silane coupling agent KH-550 and 3kg of antioxidant H911, uniformly mixing, putting into a screw extruder, setting the extrusion temperature at 60 ℃, carrying out extrusion granulation, carrying out air drying, and drying until the water content is less than or equal to 0.2%, thus obtaining the red phosphorus master batch a.
2-2, red phosphorus master batch b
The preparation method of the red phosphorus master batch b comprises the following steps:
60kg of the red phosphorus flame retardant-1 prepared in the preparation example 1 is taken, 30kg of POE elastomer (with the brand name of VM-6202), 5kg of silane coupling agent KH-550 and 5kg of antioxidant H911 are added, the mixture is uniformly mixed and then put into a screw extruder, the extrusion temperature is set to 80 ℃, the mixture is extruded and granulated and then air-dried, and the red phosphorus master batch a is obtained after the drying until the water content is less than or equal to 0.2%.
2-3, red phosphorus master batch c
The preparation method of the red phosphorus master batch c comprises the following steps:
taking 70kg of the red phosphorus flame retardant-1 prepared in the preparation example 1, adding 25kg of POE elastomer (with the trademark of DF-710), 2kg of silane coupling agent KH-550 and 3kg of antioxidant H911, uniformly mixing, putting into a screw extruder, setting the extrusion temperature to 65 ℃, carrying out extrusion granulation, carrying out air drying, and drying until the water content is less than or equal to 0.2%, thus obtaining the red phosphorus master batch a.
2-4, red phosphorus master batch d
The preparation method of the red phosphorus master batch d comprises the following steps:
taking 65kg of commercial red phosphorus flame retardant (industrial grade coated red phosphorus, the phosphorus content is more than or equal to 90wt%, and the average particle size is 2 mu m), adding 28kg of POE elastomer (with the trademark of Dow 8150), 4kg of silane coupling agent KH-550 and 3kg of antioxidant H911, uniformly mixing, putting into a screw extruder, setting the extrusion temperature at 60 ℃, carrying out extrusion granulation, carrying out air drying, and drying until the water content is less than or equal to 0.2%, thus obtaining the red phosphorus master batch d.
2-5, red phosphorus master batch e
The preparation method of the red phosphorus master batch e comprises the following steps:
taking 65kg of the red phosphorus flame retardant-2 prepared in the preparation example 1, adding 28kg of POE elastomer (with the trademark of Dow 8150), 4kg of silane coupling agent KH-550 and 3kg of antioxidant H911, uniformly mixing, putting into a screw extruder, setting the extrusion temperature at 60 ℃, carrying out extrusion granulation, carrying out air drying, and drying until the water content is less than or equal to 0.2%, thus obtaining the red phosphorus master batch e.
2-6 ammonium polyphosphate master batch
The preparation method of the ammonium polyphosphate master batch comprises the following steps:
65kg of a commercially available ammonium polyphosphate flame retardant (CAS No. 68333-79-9, model No. kpl48463, polymerization degree not less than 1000, phosphorus pentoxide not less than 71wt%, nitrogen content not less than 14wt%, and average particle size less than 20 μm) is taken, 28kg of POE elastomer (Dow 8150), 4kg of silane coupling agent KH-550 and 3kg of antioxidant H911 are added, the mixture is uniformly mixed and then put into a screw extruder, the extrusion temperature is set to 60 ℃, the mixture is extruded and granulated, then air drying is carried out, and the water content is dried to be not more than 0.2%, so that the ammonium polyphosphate master batch is obtained.
Examples
Example 1
The glass fiber reinforced flame-retardant PA66 material comprises the following components in percentage by weight: PA 6662%, glass fiber 15%, flame-retardant master batch 15%, POE-g-MAH 5%, and black master batch 3%.
In the present embodiment, the PA66 is described by taking the dupont 70G33L as an example. In this embodiment, the preferable glass fiber has a filament diameter of 11-17 μm, a filament length of 10-350 μm, and an aspect ratio (filament average length/filament average diameter) of (5-20): 1, and specifically, the alkali-free glass fiber is selected with a product number of MEF-13-1500, the filament average diameter of the fiber is 13 μm, and the filament average length is 130 μm. The flame-retardant master batch is red phosphorus master batch a. POE-g-MAH with a Dow GR216 brand, a melt index of 1.25g/10min (190 ℃, 2.16 kg) and a grafted MAH content of 0.7 percent is selected. The black master batch is prepared from Kabet PE6228 with a carbon black content of 50%.
The preparation method of the glass fiber reinforced flame-retardant PA66 material comprises the following steps:
weighing 62kg of PA66, 15kg of glass fiber, 15kg of red phosphorus master batch a, 5kg of POE-g-MAH and 3kg of black master batch, uniformly mixing the components, putting the mixture into a screw extruder, setting the first-stage temperature to be 230 ℃, the second-stage temperature to be 240 ℃, the third-stage to seventh-stage temperature to be 250 ℃ and the extrusion temperature to be 260 ℃, melting and extruding the mixture, granulating and drying until the content is less than or equal to 0.5%, and thus obtaining the glass fiber reinforced flame retardant PA66 material.
Examples 2 to 5
Examples 2-5 the amounts of the components were adjusted based on the procedure of example 1, with specific adjustment parameters as shown in table one below.
TABLE A table of the components of examples 1-5 in kg
| Components | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| PA66 | 62 | 54 | 66 | 62 | 62 |
| Glass fiber | 15 | 20 | 13 | 17 | 13 |
| Red phosphorus master batch a | 15 | 16 | 14 | 13 | 16 |
| POE-g-MAH | 5 | 6 | 4 | 5 | 6 |
| Black masterbatch | 3 | 4 | 3 | 3 | 3 |
Examples 6 to 11
Examples 6 to 11 the red phosphorus master batch a was replaced with the method of example 1. Wherein, the flame-retardant master batch in the embodiment 6 is red phosphorus master batch b; in example 7, the flame-retardant master batch is red phosphorus master batch c; in the embodiment 8, the flame-retardant master batch is red phosphorus master batch d; in the embodiment 9, the flame-retardant master batch is red phosphorus master batch e; in example 10, the flame-retardant masterbatch is ammonium polyphosphate masterbatch; the flame-retardant masterbatch in example 11 is a flame-retardant masterbatch sold by Xingyuchongwang plastics, and the model is S5000-C50.
Examples 12 to 13
Examples 12-13 the POE-g-MAH designation was changed over the procedure of example 1. Wherein, POE-g-MAH in example 12 has a mark of Exxon 1215HT, a melt index of 1.5g/10min (190 ℃, 2.16 kg), and a graft MAH content of 0.8%. The POE-g-MAH of example 13, having a trade designation Exxon VA1803, had a melt index of 2.0g/10min (190 ℃, 2.16 kg) and a grafted MAH content of 1.2%.
Example 14
Example 14 based on the method of example 1, glass fibers were conditioned, specifically alkali-free staple fibers were selected, the average filament diameter of the fibers was 13 μm, and the average filament length was 6 mm.
Examples 15 to 16
Examples 15 to 16 the black mother particles were prepared in accordance with the method of example 1. Wherein, in the embodiment 15, the black master batch is selected to be the Kabot UN6452, and the content of carbon black is 40 percent; the grade of the carbon black used in example 16 is Kabot PA3785, and the carbon black content is 30%.
Comparative example
Comparative example 1
This comparative example was conducted by adjusting the red phosphorus master batch a to red phosphorus flame retardant-1 based on the method of example 1.
Comparative example 2
This comparative example was carried out by adjusting POE-g-MAH to EPDM-g-MAH, DuPont N416, 23g/10min (280 ℃ C., 2.16 kg), based on the procedure of example 1.
Performance test
(I), UL94 flame resistance test: the glass fiber reinforced flame retardant PA66 materials prepared in examples 1-16 and comparative examples 1-2 were made into test bars with a size of 125mm x 13mm x 2mm and subjected to a vertical burning test with evaluation ratings of V0, V1 and V2, with smaller numbers indicating better flame retardant performance.
(II) low temperature resistance test: the glass fiber reinforced flame retardant PA66 materials prepared in examples 1-16 and comparative examples 1-2 were respectively and correspondingly prepared into standard test sample bars, and the notched impact strength at 23 ℃ and at-40 ℃ was respectively measured, and the test results are shown in the following table II. The test method is as follows:
(1) 23 ℃ notched impact strength: the notch impact strength of the sample strip is subjected to standard test at the temperature of 23 ℃ by adopting ASTM D256-06 impact resistance test method for plastics and electrical insulating materials, and the notch impact strength is measured by adopting a cantilever beam test method A;
(2) -rate of change of notched impact strength at 40 ℃: the standard test specimens were subjected to notched impact strength change after 144 hours at-40 ℃.
(III) electrochemical stability: the glass fiber reinforced flame retardant PA66 materials prepared in examples 1-16 and comparative examples 1-2 were prepared into test strips with a size of 50mm 25.5mm 2mm, and tested according to GB/T10064-2006, using strip electrodes with a size of 10mm 50mm, a voltage of 500V, and the test strips were placed at room temperature for resistance testing and recorded as R1Then the alloy is treated at the temperature of 200 ℃ for 24 hours and then is subjected to resistance test and recorded as R2The rate of change in resistance (%) of the test strip was recorded as = (R)1-R2）/R1100%, a smaller rate of change in resistance indicates better electrochemical stability.
TABLE II examination results of examples 1 to 16 and comparative examples 1 to 2
| UL94 flame retardant rating | Notched impact strength/KJ/m at 23 DEG C2 | -40 ℃ rate of change of notched impact strength% | Rate of change of resistance/%) | |
| Example 1 | V0 | 7.5 | 3.2 | 8.7 |
| Example 2 | V0 | 8.7 | 5.1 | 8.8 |
| Example 3 | V0 | 7.0 | 3.8 | 8.7 |
| Example 4 | V1 | 7.3 | 4.5 | 10.0 |
| Example 5 | V1 | 7.6 | 4.3 | 9.8 |
| Example 6 | V0 | 7.7 | 3.6 | 9.0 |
| Example 7 | V0 | 7.3 | 3.1 | 9.3 |
| Example 8 | V0 | 7.4 | 3.4 | 11.0 |
| Example 9 | V0 | 7.5 | 3.5 | 10.2 |
| Example 10 | V1 | 7.6 | 3.2 | 8.8 |
| Example 11 | V0 | 7.1 | 4.8 | 11.5 |
| Example 12 | V0 | 7.8 | 2.9 | 8.2 |
| Example 13 | V0 | 8.0 | 2.6 | 7.9 |
| Example 14 | V0 | 7.6 | 5.0 | 9.5 |
| Example 15 | V0 | 7.2 | 3.4 | 8.8 |
| Example 16 | V0 | 6.8 | 4.1 | 8.8 |
| Comparative example 1 | V1 | 4.6 | 10.3 | 21.5 |
| Comparative example 2 | V0 | 5.8 | 8.4 | 13.8 |
By combining the table two, comparing the results of the example 1 and the comparative examples 1-2, it can be obtained that the flame retardant master batch used in the application improves the flame retardant property of the PA66, has better compatibility with the PA66 compared with the flame retardant (comparative example 1), and can be uniformly dispersed in the PA 66; on the basis, the POE-g-MAH is also matched in the components, compared with other compatilizers (comparative example 2), the compatibility of the flame-retardant master batch and PA66 can be further improved, the fluidity of PA66 can be improved, and then glass fibers are uniformly dispersed, so that the prepared glass fiber reinforced flame-retardant PA66 material has a UL94 flame-retardant grade reaching V0 grade, and has particularly good structural strength at-40 ℃ and small change rate of notch impact strength at-40 ℃, so that the low-temperature resistance is excellent, and besides, the low resistance change rate is low, and the good electrochemical stability of nylon products can be guaranteed.
Comparing the results of examples 1-5, it can be seen that when the weight ratio of the glass fiber, the flame retardant masterbatch and the POE-g-MAH is 3:3:1, the flame retardant property, the low temperature resistance and the electrochemical stability of the prepared glass fiber reinforced flame retardant PA66 material are significantly better than those of other weight ratios, which may be because the POE-g-MAH in the composition has good stabilizing and toughening effects on the flame retardant masterbatch, ensuring that the flame retardant masterbatch can exert a flame retardant effect better, and thus the flame retardant masterbatch is further preferred. Among them, the effect of example 1 is most prominent in view of the overall effect, and therefore, it is more preferable.
Comparing the results of the embodiment 1 and the embodiments 6 to 11, it can be obtained that the flame-retardant master batch of the application is prepared by selecting the self-made red phosphorus flame retardant, the POE elastomer and other additives, and the prepared flame-retardant master batch has good chemical stability and improves the safety of the glass fiber reinforced flame-retardant PA66 material.
In example 8, the red phosphorus masterbatch is prepared from a commercially available red phosphorus flame retardant, and although the notch impact strength and the change rate of the prepared glass fiber reinforced flame retardant PA66 material are similar to those of example 1, the resistance change rate is obviously higher than that of example 1. The red phosphorus master batch of example 9 was prepared without leaving the master batch to stand, and the rate of change in resistance was also lower than that of example 1. In example 10, the flame-retardant master batch was an ammonium polyphosphate master batch, and the notched impact strength and the change rate thereof were similar to those of example 1, but the flame-retardant effect was inferior to that of example 1. The flame-retardant master batch of example 11 was a commercially available red phosphorus master batch, and the notched impact strength, the rate of change, and the rate of change in resistance were all inferior to those of example 1. Therefore, the effect of example 1 is superior to that of examples 8 to 11.
Therefore, the homemade red phosphorus master batch of this application not only can have good compatibility with PA66, can also have good insulating nature in high temperature and high humidity environment, this probably because red phosphorus is by POE elastomer parcel, and POE elastomer itself has excellent electrical insulation, still has performances such as good ageing-resistant, ozone-resistant, chemical resistance medium in addition, cooperates the antioxidant again for the system of fire-retardant master batch has good electrochemical stability.
Comparing the results of example 1 and examples 12-13, it can be seen that when the POE-g-MAH of the present application has a melt index of 1.5-2.0g/10min (190 ℃, 2.16 kg) and the grafted MAH content is 0.8-1.2%, the glass fiber reinforced flame retardant PA66 material prepared therefrom has more outstanding notched impact strength and its rate of change, and the rate of change of resistance is lower, so it is further preferred.
Comparing the results of example 1 with example 14, it can be seen that, although the glass fiber length is short, the present application has a low notched impact strength to the glass fiber reinforced flame retardant PA66 material, and on the basis of this, the rate of change of the notched impact strength can be reduced to some extent, and a modified PA66 material with more excellent electrochemical stability can be obtained.
Comparing the results of examples 1 and 15 to 16, the black masterbatch particles of the present invention are preferable because the reinforcing effect of the black masterbatch particles on PA66 can be effectively improved when the content of carbon black is not less than 40%.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The glass fiber reinforced flame-retardant PA66 material is characterized by comprising the following components in percentage by weight: PA 6654-66%, glass fiber 13-20%, flame-retardant master batch 14-16%, POE-g-MAH 4-6%, and black master batch 3-4%.
2. The glass fiber reinforced flame retardant PA66 material according to claim 1, wherein: the flame-retardant master batch is mainly prepared by extruding and granulating the following raw materials in percentage by weight: 60-70% of flame retardant, 25-30% of POE elastomer, 2-5% of silane coupling agent and 3-5% of antioxidant.
3. The glass fiber reinforced flame retardant PA66 material according to claim 2, wherein: the flame retardant is a red phosphorus flame retardant.
4. The glass fiber reinforced flame-retardant PA66 material according to claim 3, wherein the preparation method of the red phosphorus flame retardant comprises the following steps:
adding red phosphorus and a dispersing agent into water, stirring until the red phosphorus is uniformly dispersed to obtain a red phosphorus dispersion liquid, adding aluminum sulfate into the red phosphorus dispersion liquid, wherein the mass ratio of the aluminum sulfate to the red phosphorus is (3-4): 1, heating to 50 +/-2 ℃, keeping the temperature, standing for 8-10min, then continuously heating to 65 +/-2 ℃, slowly dripping a sodium carbonate solution while stirring, adjusting the pH to 5-6, keeping the temperature, reacting for 2h, cooling, filtering, washing and drying the obtained product to obtain the red phosphorus flame retardant.
5. The glass fiber reinforced flame retardant PA66 material according to claim 2, wherein: the POE elastomer is one of Dow 8150, VM-6202 and DF-710.
6. The glass fiber reinforced flame retardant PA66 material according to claim 1, wherein: the weight ratio of the glass fiber, the flame-retardant master batch and the POE-g-MAH is 3:3: 1.
7. The glass fiber reinforced flame retardant PA66 material according to claim 1, wherein: the POE-g-MAH has a melt index of 1.5-2.0g/10min (190 ℃, 2.16 kg) and a grafted MAH content of 0.8-1.2%.
8. The glass fiber reinforced flame retardant PA66 material according to claim 1, wherein: the monofilament diameter of the glass fiber is 11-17 μm, the monofilament length is 10-350 μm, and the length-diameter ratio is (5-20): 1.
9. The glass fiber reinforced flame retardant PA66 material according to claim 1, wherein: the content of carbon black in the black master batch is more than or equal to 40 percent.
10. A method for preparing the glass fiber reinforced flame-retardant PA66 material, wherein the method is used for preparing the glass fiber reinforced flame-retardant PA66 material as claimed in any one of claims 1 to 9, and comprises the following steps: weighing the components according to the set weight percentage, uniformly mixing the components, putting the mixture into a screw extruder, melting and extruding the mixture at the processing temperature of 230-260 ℃, granulating and drying to obtain the glass fiber reinforced flame retardant PA66 material.
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| CN114736513A (en) * | 2022-06-10 | 2022-07-12 | 江苏博云塑业股份有限公司 | High-bonding-wire-strength glass fiber reinforced nylon material and preparation method thereof |
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| CN105585843A (en) * | 2016-03-10 | 2016-05-18 | 广州市聚赛龙工程塑料有限公司 | Low-precipitation red-phosphorus flame-retardant nylon material and preparation method and application thereof |
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| CN105585843A (en) * | 2016-03-10 | 2016-05-18 | 广州市聚赛龙工程塑料有限公司 | Low-precipitation red-phosphorus flame-retardant nylon material and preparation method and application thereof |
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| CN114736513A (en) * | 2022-06-10 | 2022-07-12 | 江苏博云塑业股份有限公司 | High-bonding-wire-strength glass fiber reinforced nylon material and preparation method thereof |
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