CN114231025A - High-heat-resistance precipitation-resistant environment-friendly flame-retardant polyamide composition and preparation method thereof - Google Patents
High-heat-resistance precipitation-resistant environment-friendly flame-retardant polyamide composition and preparation method thereof Download PDFInfo
- Publication number
- CN114231025A CN114231025A CN202111644161.0A CN202111644161A CN114231025A CN 114231025 A CN114231025 A CN 114231025A CN 202111644161 A CN202111644161 A CN 202111644161A CN 114231025 A CN114231025 A CN 114231025A
- Authority
- CN
- China
- Prior art keywords
- mpp
- parts
- flame retardant
- precipitation
- resistant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 68
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000004952 Polyamide Substances 0.000 title claims abstract description 26
- 229920002647 polyamide Polymers 0.000 title claims abstract description 26
- 238000001556 precipitation Methods 0.000 title claims abstract description 25
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 5
- 239000004595 color masterbatch Substances 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229920006021 bio-based polyamide Polymers 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical compound CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical class [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 abstract description 24
- 239000011159 matrix material Substances 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 238000013508 migration Methods 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract 1
- FNVBALFTMLKFEC-UHFFFAOYSA-N bis(4-methyl-2-oxochromen-7-yl) phosphono phosphate Chemical compound CC1=CC(=O)OC2=CC(OP(=O)(OC3=CC=4OC(=O)C=C(C=4C=C3)C)OP(O)(O)=O)=CC=C21 FNVBALFTMLKFEC-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- 235000002245 Penicillium camembertii Nutrition 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 flame retardant modified ADP Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to a high heat-resistant precipitation-resistant environment-friendly flame-retardant polyamide composition and a preparation method thereof; the modified polyamide composite material is prepared from 30-90 parts of polyamide, 10-40 parts of filler, 0.01-30 parts of modified aluminum diethylphosphinate and a flame retardant modified MPP: 0.01-10 parts of antioxidant, 0.01-2 parts of synergist and 0.01-2 parts of color master batch. According to the environment-friendly flame-retardant polyamide with high heat resistance and precipitation resistance, the modified MPP acidity of the flame retardant is neutralized, so that the corrosion to a resin matrix in the processing process is prevented; compared with the traditional MPP, the modified MPP has fewer hydrophilic groups, so that the phenomenon of migration and precipitation of the MPP of the flame retardant can be effectively prevented; the aromatic structural group is reacted into the flame retardant through the reaction, so that the flame retardant efficiency of the flame retardant can be improved; the molecular chain of modified MPP is improved, and the decomposition of MPP in a high-temperature environment is prevented; the modified aluminum diethylphosphinate has relatively higher purity, and the heat resistance of the flame retardant can be further improved.
Description
Technical Field
The invention relates to a high-heat-resistance precipitation-resistant environment-friendly flame-retardant polyamide composition and a preparation method thereof, mainly relates to synthesis and application of a flame retardant, and belongs to the field of engineering plastic flame retardance
Background
ADP (aluminum diethylphosphinate) synergistic MPP (melamine polyphosphate) flame-retardant polyamide material belongs to halogen-free flame-retardant engineering plastics, does not contain halogen elements, does not generate harmful substances such as dioxin and the like in the combustion process, has good comprehensive mechanical properties, and is widely applied to the fields of new energy automobile battery pack modules, electronic and electrical equipment and the like.
The development of the current new energy industry is good, the battery pack is used as a core component of a new energy automobile, and the requirement on the flame retardant material of the battery pack in the module is more and more strict. However, the traditional MPP is weak in heat resistance, and is easily decomposed to form acidic substances under the action of high temperature and strong shear in the screw extrusion process, so that the plastic matrix is corroded, and the material performance is greatly weakened; after MPP acid precipitation corrodes a plastic matrix, MPP and other small molecular substances are easy to migrate to the surface of the plastic matrix at high temperature due to the damage of a polymer chain segment, so that the appearance of a workpiece is influenced; the insufficient temperature resistance of MPP can also cause decomposition and discoloration phenomena to influence the appearance after staying in a screw for a long time in the injection molding process; in addition, the generation of a by-product of sodium monoethyl hypophosphite is inevitable in the traditional ADP synthesis process, and the comprehensive stability of the flame retardant is influenced due to the relatively low heat resistance of the substances.
The improvement to the MPP temperature tolerance at present lies in promoting the whole macromolecular molecular weight of MPP more to this heat resistance that promotes MPP, but still there is free acidic group to cause the corruption to the polymer on the MPP molecular chain, and still can degrade after the macromolecule experiences high temperature strong shearing and form acid out and migration phenomenon. Neither of them relates to improvement of partial group structure of MPP to improve heat resistance and precipitation resistance of MPP.
Disclosure of Invention
The invention aims to provide a high-heat-resistance precipitation-resistant environment-friendly flame-retardant polyamide composition and a preparation method thereof, so as to solve the technical problems in the prior art.
The purpose of the invention is realized by the following technical scheme.
The high-heat-resistance precipitation-resistant environment-friendly flame-retardant polyamide composition is prepared from the following raw materials in parts by weight:
bio-based polyamide: 30-90 parts;
filling materials: 10-40 parts;
flame retardant diethyl phosphinic acid: 0.01-30 parts;
modifying MPP by using a flame retardant: 0.01-10 parts;
antioxidant: 0.01-2 parts;
the synergist comprises the following components: 0.01-2 parts;
color master batch: 0.01-2 parts.
In the high heat-resistant precipitation-resistant environment-friendly flame-retardant polyamide composition:
the polyamide comprises: polyamide materials such as PA6, PA66, PA12, PA1313, PA513, PA56PA1010, PA11, PA46 and PA 410.
The flame retardant modified MPP (melamine polyphosphate) is synthesized autonomously, and the preparation method comprises the following steps: dissolving aniline in ethanol to prepare a mixed solution, uniformly mixing the mixed solution with MPP powder, reacting the mixture of MPP and the mixed solution in a vacuum atmosphere at a pressure of 0.4-0.8 MPa and a temperature control range of 80-140 ℃ for 4-8 h, and finally reacting for 2-6 h under a pressure of-0.01-0.09 MPa or under the protection of inert gas and at a temperature of 80-180 ℃ to obtain the modified MPP. The structural formula of the finally prepared product is as follows:
wherein m and n are polymerization degrees, m is not less than 1, and n is not less than 1
This MPP is hereinafter abbreviated as BMPP
The flame retardant modified ADP (aluminum diethylphosphinate) is prepared by self, and the preparation method comprises the following steps: and nitrogen and negative pressure protection are applied in the reaction process, so that the purity of ADP is improved, the heat resistance and the flame retardant efficiency of the ADP are improved, and the specific implementation method is that nitrogen is introduced to protect the environment and the negative pressure is 0.04-0.08MPa in the ADP synthesis process. The ADP product was as follows:
the antioxidant is carried out by the main anti-auxiliary anti-synergistic effect: 1098 and 9228.
The preparation method of the high-heat-resistance precipitation-resistant environment-friendly flame-retardant polyamide composition comprises the following steps:
(1) weighing the raw materials according to the formula;
(2) adding the raw materials into a high-speed mixer together, uniformly mixing, adding into a double-screw extruder, and carrying out melting, extrusion, cooling and grain cutting by the double-screw extruder to prepare a precipitation-resistant polyamide composite material; the processing temperature of the I-X area of the double-screw extruder is 120 ℃, 200 ℃, 250 ℃, 265 ℃, 265 ℃, 265 ℃, 265 ℃, 265 ℃ and 265 ℃ in sequence. The rotating speed of the main screw is 450-500 r/min, and the temperature of the water tank is 23-50 ℃.
According to the environment-friendly flame-retardant polyamide with high heat resistance and precipitation resistance, the modified MPP acidity of the flame retardant is neutralized, so that the corrosion to a resin matrix in the processing process is prevented; compared with the traditional MPP, the modified MPP has fewer hydrophilic groups, so that the phenomenon of migration and precipitation of the MPP of the flame retardant can be effectively prevented; the aromatic structural group is reacted into the flame retardant through the reaction, so that the flame retardant efficiency of the flame retardant can be improved; the molecular chain of modified MPP is improved, and the decomposition of MPP in a high-temperature environment is prevented; the modified aluminum diethylphosphinate has relatively higher purity, and the heat resistance of the flame retardant can be further improved.
Drawings
FIG. 1 is a photograph of a comparative product from a mold deposit test on a continuous proofing board.
Detailed Description
The technical features of the present invention will be further described with reference to the following embodiments.
Firstly, carrying out synthesis modification on the used MPP, and the preparation method comprises the steps of dissolving aniline in ethanol to prepare a mixed solution, uniformly mixing the mixed solution with MPP powder, reacting the mixture of MPP and the mixed solution in a vacuum atmosphere at a pressure of 0.4-0.8 MPa and a temperature control range of 80-140 ℃ for 4-8 h, and finally reacting for 2-6 h under a pressure of-0.01-0.09 MPa or under the protection of inert gas and at a temperature of 80-180 ℃ to obtain the modified MPP. Modifying the obtained MPP into BMPP. The reaction chemical formula is as follows:
wherein n and m are more than or equal to 1.
The chemical formula shows that the amount of free H + carried by modified MPP is obviously reduced compared with that before micro-reaction, and the successful synthesis can be verified and the amount of H + ions is greatly reduced by using the number of surface hydroxyl groups (the hydroxyl groups are acidic) and measuring the PH value of the mixed solution of the flame retardant and water.
Measuring the number of surface hydroxyl groups: 2g of the product are weighed into a 200ml beaker, after which 25ml of absolute ethanol and 75ml of a 20 wt% NaCl solution are added to the beaker and stirred homogeneously, after which 0.1mol L of sodium chloride is used-1The HCl is titrated into the beaker and stirred until the PH is 4.0, and 0.1mol l is added dropwise to the beaker-1The pH of the NaOH solution is adjusted to 9.0, and the pH of the solution is kept unchanged within 20 s. The number of hydroxyl groups contained per square nanometer of the sample surface area was calculated according to the following equation.
N＝CVNA×10-3/Sm
Wherein: c is the concentration of NaOH (0.1mol L)-1) V is the volume of NaOH (mL) consumed in adjusting the pH from 4 to 9, NAIs the Avogastron constant, S is the specific surface area (nm) of the test sample2g-1) And m is the mass (g) of the sample measured.
The calculation according to the above formula shows that the number of surface hydroxyl groups of the MPP before the aniline is introduced is 6.88 per square nanometer, and the number of surface hydroxyl groups of the modified MPP obtained by introducing the aniline reaction is reduced to 1.73 per square nanometer. This demonstrates that the number of hydroxyl groups on the surface of the material is significantly reduced, which can reduce the attack of the flame retardant on the polymer matrix, and further demonstrates that the target product is obtained.
Measurement of the pH of the flame retardant: weighing 10g of MPP and BMPP in 100ml of deionized water, uniformly stirring, standing for 10min, and measuring the pH value of the mixed solution to obtain a mixed solution of modified BMPP with the pH value of 6-7 and an unmodified MPP with the pH value of 5, thereby proving that the acidity of the flame retardant is effectively improved.
Optimizing the synthesis of ADP, and introducing nitrogen protective gas and negative pressure protection with the negative pressure of 0.04-0.08MPa in the reaction process of sodium hypophosphite and ethylene, wherein the reaction process is as follows:
TGA and bulk density tests were performed on the optimized ADP powder obtained and on conventional ADP, data as follows
As can be seen from the data, the heat resistance and the volume density of the optimized ADP are improved after the ADP purity is improved, and the improvement of the volume density can be helpful for the subsequent dispersion optimization of the ADP.
After the target flame retardant is obtained, the formula is designed, and the comprehensive effect of the formula system is evaluated. .
Table 1 experimental formulation (mass fraction,%)
The formulations were granulated and tested for conventional properties as shown in the following table
The PH value of the soaking water is that 50g of plastic particles are put into 200ml of deionized water, cooled to normal temperature after being soaked in boiling water for 3h, and the PH value of the mixed solution is tested; the anti-precipitation performance is that modified material particles are used for injection molding under the conditions that the injection molding interval temperature is 275 ℃, 265 ℃ and 255 ℃, an injection molding sample plate with 150 x 100 x 1mm is injected, an experiment required for observing the appearance of white mold scale on a mold is just started, the more modulus is required for the appearance of the white mold scale, and the better anti-precipitation performance is shown.
TABLE 2 basic Properties of the formulations
Compared with formulas 1#, 2# and 3#, the flame retardant efficiency is improved along with the improvement of the addition of the traditional ADP and the traditional MPP, but the basic performance of the material is greatly influenced by the addition proportion of the flame retardant, and white substances are easily separated out to influence the appearance of a sample; compared with formulas 1#, 2#, 3# and formulas 4#, 5# and 6#, the overall material performance of the modified BMPP system is superior to that of the traditional MPP under the condition of consistent dosage of the flame retardant, and the target flame retardant efficiency can be achieved under the condition of adding a small amount of BMPP, namely the flame retardant performance of the BMPP is better; comparing formulas 1#, 2#, 3# and formulas 4#, 5#, 6#, it can be seen that the pH value of the modified material particles after using the modified BMPP is improved from the acidity before being modified to neutral, and the pH value is also reflected that the BMPP is successfully modified to weaken the acidity so as to reduce the corrosion to the plastic matrix; compared with the formulas 1#, 2#, 3# and the formulas 4#, 5# and 6#, the improved BMPP has greatly improved mobility resistance; comparing the formulations 4#, 5#, 6# and 7#, 8#, 9#, it can be seen that the flame retardancy of the material is improved after the optimized ADP is used because the effective content of ADP is improved.
And finally, carrying out long-period heat resistance on each formula system, specifically placing ISO1A dumbbell type tensile sample strips and flame-retardant sample strips with the size of 127 x 12.7 x 1.6mm of each formula system in a blowing oven at 180 ℃, respectively carrying out sampling tests on samples within 100h, 200h and 400h of aging time, and researching the mechanical property retention rate and the flame-retardant property retention rate of the material, wherein specific experimental data are as follows
TABLE 3 summary of long-term heat resistance for each formulation
Compared with formulas 1#, 2#, 3# and formulas 4#, 5# and 6#, the optimized BMPP has better material mechanical property retention rate in a long-period thermo-oxidative aging environment, because free acid groups on the BMPP are reacted, the corrosion effect on resin is far smaller than that of the traditional MPP, and a benzene ring structure is introduced on the structure, so that a molecular chain is more stable, the material property reduction caused by the molecular migration of the BMPP is prevented, the heat resistance of the flame retardant is improved, and a sample can still keep good flame retardant property under the same flame retardant adding content and thermo-oxidative aging condition; compared with formulas 4#, 5#, 6# and formulas 7#, 8# and 9#, the ADP prepared by the method and optimized in the synthesis process is superior to the traditional ADP in thermal stability in the use process, namely the ADP has better performance retention rate and better flame retardant stability in a long-period thermal oxidation aging atmosphere.
TABLE 4 summary of long-term heat and flame retardant properties for each formulation
According to the environment-friendly flame-retardant polyamide with high heat resistance and precipitation resistance, the modified MPP acidity of the flame retardant is neutralized, so that the corrosion to a resin matrix in the processing process is prevented; compared with the traditional MPP, the modified MPP has fewer hydrophilic groups, so that the phenomenon of migration and precipitation of the MPP of the flame retardant can be effectively prevented; the aromatic structural group is reacted into the flame retardant through the reaction, so that the flame retardant efficiency of the flame retardant can be improved; the molecular chain of modified MPP is improved, and the decomposition of MPP in a high-temperature environment is prevented; the modified aluminum diethylphosphinate has relatively higher purity, and the heat resistance of the flame retardant can be further improved.
Claims (6)
1. The high-heat-resistance precipitation-resistant environment-friendly flame-retardant polyamide composition is characterized in that: the material is prepared from the following raw materials in parts by weight:
bio-based polyamide: 30-90 parts;
filling materials: 10-40 parts;
flame retardant diethyl phosphinic acid: 0.01-30 parts;
modifying MPP by using a flame retardant: 0.01-10 parts;
antioxidant: 0.01-2 parts;
the synergist comprises the following components: 0.01-2 parts;
color master batch: 0.01-2 parts.
2. The high heat-resistant precipitation-resistant environment-friendly flame-retardant polyamide composition as claimed in claim 1, wherein: the polyamide comprises: PA6, PA66, PA12, PA1313, PA513, PA56PA1010, PA11, PA46 and PA410 polyamide materials.
3. The high heat-resistant precipitation-resistant environment-friendly flame-retardant polyamide composition as claimed in claim 1, wherein: the flame retardant modified MPP is synthesized autonomously, and the preparation method comprises the following steps: dissolving aniline in ethanol to prepare a mixed solution, uniformly mixing the mixed solution with MPP powder, reacting the mixture of MPP and the mixed solution in a vacuum atmosphere at a pressure of 0.4-0.8 MPa and a temperature control range of 80-140 ℃ for 4-8 h, and finally reacting for 2-6 h under a pressure of-0.01-0.09 MPa or under the protection of inert gas and at a temperature of 80-180 ℃ to obtain modified MPP; the structural formula of the finally prepared product is as follows:
wherein m and n are polymerization degrees, m is more than or equal to 1, and n is more than or equal to 1.
4. The high heat-resistant precipitation-resistant environment-friendly flame-retardant polyamide composition as claimed in claim 1, wherein: the flame retardant modified ADP is self-made, and the preparation method comprises the following steps: nitrogen and negative pressure protection are applied in the reaction process, so that the purity of ADP is improved, the heat resistance and the flame retardant efficiency of the ADP are improved, and the specific implementation method is that the negative pressure of nitrogen protective gas environment is 0.04-0.08MPa in the ADP synthesis process; the ADP product was as follows:
5. the high heat-resistant precipitation-resistant environment-friendly flame-retardant polyamide composition as claimed in claim 1, wherein: the antioxidant is carried out by the main anti-auxiliary anti-synergistic effect: 1098 and 9228.
6. The preparation method of the high heat-resistant precipitation-resistant environment-friendly flame-retardant polyamide composition as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
(1) weighing the raw materials according to the formula;
(2) adding the raw materials into a high-speed mixer together, uniformly mixing, adding into a double-screw extruder, and carrying out melting, extrusion, cooling and grain cutting by the double-screw extruder to prepare a precipitation-resistant polyamide composite material; the processing temperature of the I-X area of the double-screw extruder is 120 ℃, 200 ℃, 250 ℃, 265 ℃, 265 ℃, 265 ℃, 265 ℃, 265 ℃ and 265 ℃ in sequence. The rotating speed of the main screw is 450-500 r/min, and the temperature of the water tank is 23-50 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111644161.0A CN114231025A (en) | 2021-12-29 | 2021-12-29 | High-heat-resistance precipitation-resistant environment-friendly flame-retardant polyamide composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111644161.0A CN114231025A (en) | 2021-12-29 | 2021-12-29 | High-heat-resistance precipitation-resistant environment-friendly flame-retardant polyamide composition and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114231025A true CN114231025A (en) | 2022-03-25 |
Family
ID=80744504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111644161.0A Pending CN114231025A (en) | 2021-12-29 | 2021-12-29 | High-heat-resistance precipitation-resistant environment-friendly flame-retardant polyamide composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114231025A (en) |
-
2021
- 2021-12-29 CN CN202111644161.0A patent/CN114231025A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Performance of intumescent flame retardant master batch synthesized through twin-screw reactively extruding technology: effect of component ratio | |
| CN110054807B (en) | Phosphorus-nitrogen halogen-free flame retardant composition for improving thermal stability by using inorganic metal phosphite and application thereof | |
| CN109880248B (en) | Methyl octabromoether flame-retardant polystyrene composite material and preparation method thereof | |
| US7491763B2 (en) | Polyamide composition | |
| CN112457623B (en) | High-impact-resistance and yellowing-resistance flame-retardant ABS material and preparation method thereof | |
| JPWO2005068558A1 (en) | Flame retardant and flame retardant resin composition | |
| CN111825883A (en) | Metal complex salts of polydialkylphosphinic acids and/or mixtures thereof, and use thereof | |
| CN115260754A (en) | High-toughness halogen-free flame-retardant PA66 material and preparation method thereof | |
| CN112608592A (en) | High-dispersibility high-concentration nylon-based halogen-free flame-retardant master batch and preparation method thereof | |
| CN111201286B (en) | Polyamide resin composition and molded article obtained by molding same | |
| CN115011087B (en) | Flame-retardant polyester foam board and preparation method thereof | |
| CN113321873B (en) | Low-shrinkage high-toughness modified polypropylene material and preparation method thereof | |
| CN114539618B (en) | Silicone rubber halogen-free flame retardant, and preparation method and application thereof | |
| CN114989557A (en) | High-temperature-resistant modified ABS plastic and preparation method thereof | |
| CN109280259B (en) | EVA/PA6 flame-retardant composite material added with OMMT in distribution regulation and control mode and preparation method | |
| EP4215575A1 (en) | Halogen-free flame-retardant compounded system having resistance to high heat and high shear and high flame resistance, and application thereof | |
| CN114479442A (en) | Anti-freezing liquid precipitation-resistant flame-retardant bio-based polyamide composition and preparation method thereof | |
| CN111961340B (en) | Halogen-free flame-retardant bio-based nylon 56 composite material and preparation method thereof | |
| CN114231025A (en) | High-heat-resistance precipitation-resistant environment-friendly flame-retardant polyamide composition and preparation method thereof | |
| CN109181294B (en) | Method for improving high temperature thermal stability of thermoplastic polymers or composites thereof using inorganic and alkyl metal salts of phosphorous acid | |
| EP3971228B1 (en) | Polyamide resin composition | |
| CN108587148A (en) | A method of preparing 6 fire proofing of fiberglass reinforced PA | |
| CN114316584B (en) | Brominated flame-retardant high-heat-resistance bio-based polyamide composition and preparation method thereof | |
| CN114196203B (en) | Red phosphorus flame-retardant compound and preparation method and application thereof | |
| WO2018123563A1 (en) | Polyamide resin composition, method for producing same and molded body formed from same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220325 |