CN113265141A - Antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material, preparation method and application - Google Patents
Antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material, preparation method and application Download PDFInfo
- Publication number
- CN113265141A CN113265141A CN202010156276.4A CN202010156276A CN113265141A CN 113265141 A CN113265141 A CN 113265141A CN 202010156276 A CN202010156276 A CN 202010156276A CN 113265141 A CN113265141 A CN 113265141A
- Authority
- CN
- China
- Prior art keywords
- antimony
- retardant
- flame
- composite material
- phenylene terephthalamide
- 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
- 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 97
- 239000003063 flame retardant Substances 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 239000003365 glass fiber Substances 0.000 claims abstract description 22
- 238000001125 extrusion Methods 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000012745 toughening agent Substances 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 18
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 9
- 238000007605 air drying Methods 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 9
- 238000004806 packaging method and process Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229940126062 Compound A Drugs 0.000 claims description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- ZDZYGYFHTPFREM-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypropan-1-amine Chemical compound NCCC[Si](OC)(OC)OCCCN ZDZYGYFHTPFREM-UHFFFAOYSA-N 0.000 claims description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 5
- 229960001545 hydrotalcite Drugs 0.000 claims description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 5
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 229910017059 organic montmorillonite Inorganic materials 0.000 claims description 4
- -1 polyparaphenylene terephthalamide Polymers 0.000 claims description 4
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 238000011089 mechanical engineering Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 150000003918 triazines Chemical class 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 238000005469 granulation Methods 0.000 abstract description 2
- 230000003179 granulation Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 11
- 239000004677 Nylon Substances 0.000 description 8
- 229920001778 nylon Polymers 0.000 description 8
- 229910052787 antimony Inorganic materials 0.000 description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005389 magnetism Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- RPJGYLSSECYURW-UHFFFAOYSA-K antimony(3+);tribromide Chemical compound Br[Sb](Br)Br RPJGYLSSECYURW-UHFFFAOYSA-K 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
Abstract
The invention belongs to the technical field of high polymer materials, and discloses an antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material, a preparation method and application thereof, wherein the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material comprises 36-60 wt% of PPA resin, 15-20 wt% of a brominated flame retardant, 3-8 wt% of a compound flame-retardant synergist, 3-5 wt% of a toughening agent, 0.2-0.6 wt% of an antioxidant, 0.2-0.8 wt% of other additives and 10-40 wt% of glass fibers, all the components are mixed in a high-speed mixer for 3-5 minutes and then placed in a double-screw extruder for extrusion and granulation, and the glass fiber side feeding is carried out. The PPA resin has the advantages of improving the mechanical strength and the heat resistance of the PPA resin, improving the flame retardant grade of the PPA resin, enabling the PPA resin to meet UL94V0 and 5VA grades, having the characteristics of rapid forming, high cost performance and the like, and greatly expanding the application field of the PPA resin in electronic appliances.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material, and a preparation method and application thereof.
Background
The poly (p-phenylene terephthalamide) (PPA) resin is a semi-aromatic polyamide made from terephthalic acid or p-phenylenediamine. The PPA resin has excellent comprehensive performance and good performances in the aspects of heat, electricity, physics and chemical resistance. Particularly, the PPA resin still has high rigidity and high strength and excellent dimensional accuracy and stability at high temperature, so that the PPA resin has wide application prospects in the fields of automobiles, electronics, electrics, mechanical engineering and the like.
However, the poly (p-phenylene terephthalamide) resin also has some disadvantages, which limit the further expansion of the application field. For example, poly (p-phenylene terephthalamide) is a flammable material and does not meet the UL94V0 rating. With the improvement of safety awareness and the deepening of fire protection awareness, materials with flame retardancy of more than V0 are required to be used for various parts of electrical equipment, instruments, buildings and the like. In addition, the mechanical property and the temperature resistance of the poly-terephthaloyl-p-phenylenediamine (PPA) which is not reinforced and modified by the glass fiber are lower, the mechanical property and the heat resistance of the PPA can be greatly improved through the glass fiber reinforcement, and the application range of the PPA in electronic and electric appliances can be expanded. Therefore, the flame retardant enhancement modification of the poly-terephthaloyl-p-phenylenediamine is carried out, the flame retardant grade and the mechanical property of the poly-terephthaloyl-p-phenylenediamine resin are improved, and the expansion of the application range is very important.
Chuzhou Jisheng new material science and technology limited company discloses a patent of 'flame-retardant reinforced high-temperature nylon and a preparation method thereof (CN 109504074A)', the flame-retardant reinforced high-temperature nylon is prepared by synergistic preparation of a brominated flame retardant and an antimony auxiliary flame retardant, the brominated flame retardant and an antimony compound are used for synergistic flame retardance, and the flame-retardant reinforced high-temperature nylon is prepared, but the patent does not have clear data for evaluating the material performance; shanghai Jie Shijie New materials (group) member company discloses a patent of ' a flame-retardant reinforced high-temperature-resistant nylon composite material and a preparation method thereof ' (CN106566234A) ', wherein the flame-retardant reinforced high-temperature nylon is prepared by modifying a flame retardant with a rare earth compound, then adding high-temperature nylon and glass fiber, the flame retardance reaches V0, the mechanical property is excellent, but the cost is high due to the use of the rare earth compound modified flame retardant; although the two patents can prepare the high-performance flame-retardant reinforced high-temperature nylon material, antimony oxide is used as a flame-retardant synergist to improve the flame-retardant effect, antimony is a non-renewable resource, and antimony is a heavy metal which can cause harm to human health and environment, and more countries, regions and industry fields are limited and forbidden to use antimony and antimony compounds. Therefore, the development of a flame-retardant high-temperature nylon material which does not contain antimony, can meet the flame-retardant requirement V0 and has excellent performance is urgently needed.
In summary, the problems of the prior art are as follows: the existing flame-retardant reinforced PPA material antimony bromide flame-retardant system has the defect that antimony oxide must be added, and the defects that the mechanical property of unmodified PPA resin is not high, the thermal deformation temperature is low, and the flame retardance cannot reach V0 can be solved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material, a preparation method and application thereof. The invention aims to provide an antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material and a preparation method thereof, which solve the defect that antimony oxide must be added into a bromine-antimony flame-retardant system of the existing flame-retardant reinforced PPA material, simultaneously solve the defects that unmodified PPA resin has low mechanical property, low thermal deformation temperature and flame retardance of V0, develop the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material, greatly widen the application of the PPA material in the fields of electronic appliances, automobiles and the like, reduce the dependence on antimony and strengthen the environmental protection.
The invention is realized in such a way that the antimony-free flame-retardant reinforced poly-p-phenylene terephthalamide composite material comprises, by weight, 39% -60% of PPA resin, 15% -20% of a brominated flame retardant, 3% -8% of a compound flame-retardant synergist, 3% -5% of a toughening agent, 0.2% -0.6% of an antioxidant, 0.2% -0.8% of other auxiliary agents and 10% -40% of glass fibers.
Further, the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material. The poly-p-phenylene terephthamide resin is baked at 140 deg.C for 4 hr before use to control the water content below 0.1%.
Further, the brominated flame retardant is one or more of brominated epoxy resin with the molecular weight of 25000-30000, brominated polystyrene particles, decabromodiphenylethane or brominated triazine.
Further, the toughening agent is one or two of glycidyl methacrylate grafted ethylene-octene copolymer and ethylene-butyl acrylate-glycidyl methacrylate copolymer.
Further, the antioxidant is a sterically hindered phenol antioxidant, and comprises one or two of an antioxidant 1098 and an antioxidant 168.
Further, the other auxiliary agents are a lubricant and a heat stabilizer.
Further, the glass fiber is twistless roving with the surface being subjected to impregnation coating by a silane-based agent.
The invention also aims to provide a preparation method of the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material, which comprises the following steps:
firstly, mixing the dried PPA resin, the brominated flame retardant, the compound flame-retardant synergist, the toughening agent, the antioxidant and other auxiliaries in a high-speed mixer to fully stir and uniformly disperse all the components;
secondly, adding the mixed materials into a double-screw extruder for melt extrusion, wherein the melt extrusion temperature is 260-300 ℃, and the screw rotating speed is 300-500 r/m;
and thirdly, cooling, air-drying, granulating, strongly magnetizing and packaging the extruded material to obtain a finished product.
Further, the preparation method of the compound flame-retardant synergist comprises the following steps:
(1) dissolving organic montmorillonite in deionized water, and gradually adding tribromophenol intermediate under high-speed stirring and ultrasonic dispersion conditions; reacting for 5-6 h at 75-80 ℃, filtering, removing deionized water, and drying to obtain a compound A of tribromophenol intermediate intercalated montmorillonite;
(2) uniformly mixing the compound A, hydrotalcite and anhydrous zinc borate, stirring at 500r/min, spraying a 2-aminoethyl-aminopropyl trimethoxy silane coupling agent during stirring, coating the mixture, and cooling to obtain the compound flame retardant synergist.
The invention also aims to provide application of the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material in automobile, electronic and electric connector and mechanical engineering structural parts.
In summary, the advantages and positive effects of the invention are: the antimony-free flame-retardant reinforced poly-p-phenylene terephthalamide composite material can improve the mechanical strength and the heat resistance of PPA resin, simultaneously improve the flame-retardant grade of the PPA resin, enable the PPA resin to reach UL94V0 and 5VA grades, simultaneously have the characteristics of quick forming, high cost performance and the like, and greatly expand the application field of the PPA resin.
Drawings
FIG. 1 is a flow chart of a method for preparing an antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides an antimony-free flame-retardant reinforced poly (terephthaloyl-p-phenylenediamine) composite material, a preparation method and application thereof, and the invention is described in detail with reference to the accompanying drawings.
The antimony-free flame-retardant reinforced poly-p-phenylene terephthalamide composite material provided by the embodiment of the invention comprises, by weight, 39-60% of PPA resin, 15-20% of a brominated flame retardant, 3-8% of a compound flame-retardant synergist, 3-5% of a toughening agent, 0.2-0.6% of an antioxidant, 0.2-0.8% of other auxiliaries and 10-40% of glass fibers.
In the preferred embodiment of the invention, the melting point of the poly-terephthaloyl-p-phenylenediamine resin is 310 ℃, the molecular weight is 5-8W, and the poly-terephthaloyl-p-phenylenediamine resin needs to be baked at 140 ℃ for 4 hours before use, so that the water content is controlled to be below 0.1 percent.
In a preferred embodiment of the invention, the brominated flame retardant is one or more of brominated epoxy resin with a molecular weight of 25000-30000, brominated polystyrene particles, decabromodiphenylethane or brominated triazine.
In the preferred embodiment of the invention, the compound flame-retardant synergist is self-made, and the compound flame-retardant synergist is self-made. According to the mass percentage, the 5000-mesh anhydrous zinc borate is 20-25%, the 5000-mesh hydrotalcite is 15-20%, the 5000-mesh octadecylamine treated organic montmorillonite is 15-20%, the tribromophenol intermediate is 20-25%, and the 5-10% 2-aminoethyl-aminopropyltrimethoxysilane coupling agent is prepared by the following steps:
a: dissolving organic montmorillonite in deionized water, and gradually adding tribromophenol intermediate under high-speed stirring and ultrasonic dispersing conditions. Reacting for 5-6 h at 75-80 ℃, filtering, removing deionized water, and drying to obtain the compound A of the tribromophenol intermediate intercalated montmorillonite.
B: uniformly mixing the compound A, hydrotalcite and anhydrous zinc borate, stirring at a high speed (500r/min), spraying a 2-aminoethyl-aminopropyltrimethoxysilane coupling agent in proportion during stirring, coating the mixture, and cooling to obtain the compound flame-retardant synergist.
In the preferred embodiment of the invention, the toughening agent is one or two of glycidyl methacrylate grafted ethylene-octene copolymer and ethylene-butyl acrylate-glycidyl methacrylate copolymer.
In a preferred embodiment of the present invention, the antioxidant is a sterically hindered phenolic antioxidant, including one or both of antioxidant 1098 and antioxidant 168.
In a preferred embodiment of the invention, further auxiliaries are lubricants and heat stabilizers.
In a preferred embodiment of the invention, the glass fibers are twistless rovings that are surface-size coated with a silane-based agent.
As shown in fig. 1, a preparation method of an antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material provided by an embodiment of the present invention includes the following steps:
s101: treatment and mixing of raw materials: mixing the dried PPA resin, the brominated flame retardant, the compound flame-retardant synergist, the toughening agent, the antioxidant and other auxiliaries in a high-speed mixer, and fully stirring and uniformly dispersing all the components;
s102: melt extrusion: adding the mixed materials into a double-screw extruder for melt extrusion, wherein the melt extrusion temperature is 260-300 ℃, and the screw rotating speed is 300-500 r/m;
s103: granulation and post-treatment: and cooling, air-drying, granulating, strong magnetic treatment and packaging the extruded material to obtain a finished product.
The technical solution of the present invention is further described with reference to the following specific examples.
Example 1
The preparation method of the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material provided by the embodiment of the invention comprises the following steps: the PPA resin with the weight of 60 percent is baked for 4 hours at the temperature of 120 ℃ to control the water content to be below 0.1 percent, and then mixed with 17 percent of decabromodiphenylethane flame retardant, 8 percent of flame-retardant synergist, 4 percent of flexibilizer, 0.2 percent of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine (1098) and 0.2 percent of tris- (2, 4-di-tert-butylphenyl) phosphite (168) by weight, and 0.6 percent of other assistants by weight through a high-speed mixer for 3 minutes, and then the mixed materials enter a double-screw extruder from a metering feeder and are plasticized and melted with 10 percent of glass fiber by weight added from a glass fiber feeding port, and then the product is obtained through extrusion, cooling, air drying, grain cutting, super-strong magnetism and packaging. Wherein the melt extrusion temperature is 260-300 ℃, and the rotating speed of the screw is 400 r/min.
Example 2
The preparation method of the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material provided by the embodiment of the invention comprises the following steps: firstly, 55 percent of PPA resin by weight is dried at 120 ℃ for 4 hours, the water content is controlled below 0.1 percent, and then the PPA resin is mixed with 15 percent of decabromodiphenylethane flame retardant by weight, 6 percent of flame retardant synergist by weight, 3 percent of flexibilizer by weight, 0.2 percent of N, N' -bis- (3-3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine (1098) by weight, 0.2 percent of tris- (2, 4-di-tert-butylphenyl) phosphite (168) by weight and 0.6 percent of other auxiliary agents by weight through a high-speed mixer for 3 minutes, and then the mixture enters a double-screw extruder from a metering feeder to be plasticized and melted with 20 percent of glass fiber by weight added from a glass fiber feeding port, and then the product is obtained through extrusion, cooling, air drying, grain cutting, super-strong magnetism and packaging. Wherein the melt extrusion temperature is 260-300 ℃, and the rotating speed of the screw is 400 r/min.
Example 3
The preparation method of the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material provided by the embodiment of the invention comprises the following steps: firstly, 48 percent of PPA resin by weight is baked at 120 ℃ for 4 hours, the water content is controlled below 0.1 percent, and then the PPA resin is mixed with 13 percent of decabromodiphenylethane flame retardant by weight, 5 percent of flame retardant synergist by weight, 3 percent of flexibilizer by weight, 0.2 percent of N, N' -bis- (3-3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine (1098) by weight, 0.2 percent of tris- (2, 4-di-tert-butylphenyl) phosphite (168) by weight and 0.6 percent of other auxiliaries by weight through a high-speed mixer for 3 minutes, then the mixture enters a double-screw extruder from a metering feeder and is plasticized and melted with 30 percent of glass fiber added from a glass fiber feeding port, and then the product is obtained through extrusion, cooling, air drying, grain cutting, super-strong magnetism and packaging. Wherein the melt extrusion temperature is 260-300 ℃, and the rotating speed of the screw is 400 r/min.
Example 4
The preparation method of the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material provided by the embodiment of the invention comprises the following steps: the PPA resin with the weight of 41 percent is baked for 4 hours at the temperature of 120 ℃ to control the water content to be below 0.1 percent, and then mixed with 11 percent of decabromodiphenylethane flame retardant, 4 percent of flame retardant synergist, 3 percent of flexibilizer, 0.2 percent of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine (1098), 0.2 percent of tris- (2, 4-di-tert-butylphenyl) phosphite (168) and 0.6 percent of other auxiliary agents by weight through a high-speed mixer for 3 minutes, and then the mixture enters a double-screw extruder from a metering feeder to be plasticized and melted with 40 percent of glass fiber by weight added from a glass fiber feeding port, and then the product is obtained through extrusion, cooling, air drying, grain cutting, super-strong magnetism and packaging. Wherein the melt extrusion temperature is 260-300 ℃, and the rotating speed of the screw is 400 r/min.
The technical effects of the present invention will be described in detail with reference to the tests below.
Comparative example 1
The preparation method of the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material provided by the embodiment of the invention comprises the following steps: firstly, 53 percent of PPA resin by weight is dried at 120 ℃ for 4 hours, the water content is controlled below 0.1 percent, and then the PPA resin, 13 percent of decabromodiphenylethane flame retardant by weight, 3 percent of toughening agent by weight, 0.2 percent of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine (1098) by weight, 0.2 percent of tris- (2, 4-di-tert-butylphenyl) phosphite (168) by weight and 0.6 percent of other auxiliary agents by weight are mixed by a high-speed mixer for 3 minutes, then the mixture enters a double-screw extruder from a metering feeder and is plasticized and melted with 30 percent of glass fiber by weight added from a glass fiber adding port, and then the product is obtained by extrusion, cooling, air drying, grain cutting, strong magnetism and packaging. Wherein the melt extrusion temperature is 260-300 ℃, and the rotating speed of the screw is 400 r/min.
Comparative example 2
The preparation method of the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material provided by the embodiment of the invention comprises the following steps: 48% by weight of PPA resin was first baked at 120 ℃ for 4 hours to control the water content to 0.1% or less, and then plasticized together with 13% by weight of decabromodiphenylethane flame retardant, 1.2% by weight of 5000 mesh anhydrous zinc borate, 1.0% by weight of 5000 mesh hydrotalcite, 1.0% by weight of 5000 mesh octadecylamine-treated organo montmorillonite, 1.2% by weight of tribromophenol intermediate, 0.6% by weight of 2-aminoethyl-aminopropyltrimethoxysilane coupling agent, 3% by weight of toughening agent, 0.2% by weight of N, N' -bis- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl) hexanediamine (1098) and 0.2% by weight of tris- (2, 4-di-t-butylphenyl) phosphite (168), 0.6% by weight of other auxiliaries by weight of a high-speed mixer for 3 minutes, then fed from a metering twin-screw extruder and 30% by weight of glass fibers fed from a feeding port, Melting, extruding, cooling, air drying, granulating, strong magnetic treatment and packaging to obtain the product. Wherein the melt extrusion temperature is 260-300 ℃, and the rotating speed of the screw is 400 r/min.
The antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite materials prepared in examples 1 to 4 were subjected to performance tests, and the results are shown in table 1:
table 1 results of composite property tests of examples 1 to 4 and comparative examples 1 to 2
Through the test data of the examples 1 to 4 and the comparative example 1, the self-made flame retardant synergist can effectively improve the flame retardant effect and achieve the aim of V0. It can be seen from example 3 and comparative example 2 that the addition of the untreated flame retardant synergist to the formulation, although it also has a flame retardant effect, can only satisfy the requirement of V1, and at the same time, has a negative effect on the material properties and reduces the mechanical properties.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material is characterized by comprising 39-60 wt% of PPA resin, 15-20 wt% of a brominated flame retardant, 3-8 wt% of a compound flame-retardant synergist, 3-5 wt% of a toughening agent, 0.2-0.6 wt% of an antioxidant, 0.2-0.8 wt% of other auxiliaries and 10-40 wt% of glass fibers.
2. The antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material according to claim 1, wherein the moisture content of the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material is controlled to be less than 0.1% by baking the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material for 4 hours at 140 ℃ before use.
3. The antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material according to claim 1, wherein the bromine-based flame retardant is one or more of brominated epoxy resin with a molecular weight of 25000-30000, brominated polystyrene particles, decabromodiphenylethane or brominated triazine.
4. The antimony-free flame retardant reinforced polyparaphenylene terephthalamide composite material according to claim 1, wherein the toughening agent is one or both of glycidyl methacrylate grafted ethylene-octene copolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer.
5. The antimony-free flame retardant reinforced poly (p-phenylene terephthalamide) composite material of claim 1, wherein the antioxidant is a sterically hindered phenolic antioxidant comprising one or both of antioxidant 1098 and antioxidant 168.
6. The antimony-free flame retardant reinforced poly (p-phenylene terephthalamide) composite of claim 1, wherein the other additives are lubricants and heat stabilizers.
7. The antimony-free flame retardant reinforced poly (p-phenylene terephthalamide) composite of claim 1, wherein the glass fibers are twistless rovings that are surface-size coated with a silane based agent.
8. A method for preparing the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material according to claim 1, wherein the method for preparing the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material comprises the following steps:
firstly, mixing the dried PPA resin, the brominated flame retardant, the compound flame-retardant synergist, the toughening agent, the antioxidant and other auxiliaries in a high-speed mixer to fully stir and uniformly disperse all the components;
secondly, adding the mixed materials into a double-screw extruder for melt extrusion, wherein the melt extrusion temperature is 260-300 ℃, and the screw rotating speed is 300-500 r/m;
and thirdly, cooling, air-drying, granulating, strongly magnetizing and packaging the extruded material to obtain a finished product.
9. The preparation method of the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material according to claim 8, wherein the preparation method of the compound flame-retardant synergist comprises the following steps:
(1) dissolving organic montmorillonite in deionized water, and gradually adding tribromophenol intermediate under high-speed stirring and ultrasonic dispersion conditions; reacting for 5-6 h at 75-80 ℃, filtering, removing deionized water, and drying to obtain a compound A of tribromophenol intermediate intercalated montmorillonite;
(2) uniformly mixing the compound A, hydrotalcite and anhydrous zinc borate, stirring at 500r/min, spraying a 2-aminoethyl-aminopropyltrimethoxysilane coupling agent during stirring, coating the mixture, and cooling to obtain the compound flame-retardant synergist.
10. The use of the antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material according to any one of claims 1 to 7 in automobiles, electronic and electrical products and mechanical engineering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010156276.4A CN113265141A (en) | 2020-03-08 | 2020-03-08 | Antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010156276.4A CN113265141A (en) | 2020-03-08 | 2020-03-08 | Antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113265141A true CN113265141A (en) | 2021-08-17 |
Family
ID=77227578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010156276.4A Pending CN113265141A (en) | 2020-03-08 | 2020-03-08 | Antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113265141A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508843A (en) * | 2008-12-23 | 2009-08-19 | 深圳市科聚新材料有限公司 | Halogen-free flame-proof reinforced poly-terephthaloyl para-phenylene diamine composite material |
| CN104693793A (en) * | 2014-12-15 | 2015-06-10 | 深圳市富恒新材料股份有限公司 | Flame-retardant reinforced nylon composite material and preparation method thereof |
| CN107418156A (en) * | 2017-04-21 | 2017-12-01 | 金旸（厦门）新材料科技有限公司 | A kind of high glow-wire enhancing flame retardant type PBT composite and preparation method thereof |
| CN108948734A (en) * | 2018-05-31 | 2018-12-07 | 徐州腾飞工程塑料有限公司 | A kind of high glowing filament ignition temperature flame-retardant enhancing PA6 composite material and preparation method |
| CN109385071A (en) * | 2018-11-13 | 2019-02-26 | 苏州亨利通信材料有限公司 | A kind of flame retardant property reaches the TPU material and preparation method thereof of vertical combustion V0 grade |
| CN110387124A (en) * | 2019-07-09 | 2019-10-29 | 广东奇德新材料股份有限公司 | A kind of halogen-free flame-proof reinforced poly phthalamide composite material and preparation method |
-
2020
- 2020-03-08 CN CN202010156276.4A patent/CN113265141A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508843A (en) * | 2008-12-23 | 2009-08-19 | 深圳市科聚新材料有限公司 | Halogen-free flame-proof reinforced poly-terephthaloyl para-phenylene diamine composite material |
| CN104693793A (en) * | 2014-12-15 | 2015-06-10 | 深圳市富恒新材料股份有限公司 | Flame-retardant reinforced nylon composite material and preparation method thereof |
| CN107418156A (en) * | 2017-04-21 | 2017-12-01 | 金旸（厦门）新材料科技有限公司 | A kind of high glow-wire enhancing flame retardant type PBT composite and preparation method thereof |
| CN108948734A (en) * | 2018-05-31 | 2018-12-07 | 徐州腾飞工程塑料有限公司 | A kind of high glowing filament ignition temperature flame-retardant enhancing PA6 composite material and preparation method |
| CN109385071A (en) * | 2018-11-13 | 2019-02-26 | 苏州亨利通信材料有限公司 | A kind of flame retardant property reaches the TPU material and preparation method thereof of vertical combustion V0 grade |
| CN110387124A (en) * | 2019-07-09 | 2019-10-29 | 广东奇德新材料股份有限公司 | A kind of halogen-free flame-proof reinforced poly phthalamide composite material and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111662538B (en) | Low-smoke-density high-performance halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) compound and preparation method thereof | |
| CN107418201B (en) | Efficient halogen-free flame-retardant reinforced nylon composite material and preparation method thereof | |
| CN104672897A (en) | Flame-retardant heat-conduction anti-static nylon 66 composite material and preparation method thereof | |
| CN111748179B (en) | Low-smoke-density high-performance halogen-containing flame-retardant reinforced PBT (polybutylene terephthalate) compound and preparation method thereof | |
| CN102093651B (en) | Inflaming retarding electromagnetic shielding polyvinyl chloride material and production method thereof as well as electrician sleeve | |
| CN101070426A (en) | Glass-fiber reinforced fire-retardant polyamide resin composition | |
| CN112457623B (en) | High-impact-resistance and yellowing-resistance flame-retardant ABS material and preparation method thereof | |
| CN111171562A (en) | Halogen-free flame-retardant glass fiber reinforced nylon material and preparation method thereof | |
| CN111334039A (en) | Reinforced polyamide 66 composition and method for making same | |
| CN107541049B (en) | Graphene-continuous glass fiber reinforced halogen-free flame-retardant weather-resistant PPO/HIPS alloy material and preparation method thereof | |
| WO2022110665A1 (en) | Flame-retardant antistatic polyamide composite material, preparation method therefor, and use thereof | |
| CN104164084A (en) | Glass-fiber-enhanced nylon 66/nylon 6 composite material preparation method | |
| CN111484739A (en) | Flame-retardant reinforced polyamide composition and preparation method thereof | |
| CN108530887B (en) | High-heat-resistance and high-strength semi-aromatic polyamide/polyester alloy material and preparation method and application thereof | |
| CN104262955A (en) | High-GWIT carbon fiber reinforced halogen-free flame-retardant PA46 composite material and preparation thereof | |
| CN109280259B (en) | EVA/PA6 flame-retardant composite material added with OMMT in distribution regulation and control mode and preparation method | |
| CN112457664A (en) | Flame-retardant polyamide composite material and preparation method and application thereof | |
| CN110194893B (en) | Silicon-aluminum compound and magnesium hydroxide synergistic flame-retardant nylon composite material and preparation method thereof | |
| CN108424642A (en) | One kind can laser engraving fire-retardant nylon PA66 materials and preparation method thereof | |
| CN111423723A (en) | Reinforced polyphenylene sulfide composition for 5G and preparation method thereof | |
| CN111484731A (en) | High-modulus flame-retardant reinforced nylon composite material and preparation method thereof | |
| CN101921472A (en) | High impact-resistant halogen-free flame-retardant reinforced nylon material and preparation method thereof | |
| CN111117060A (en) | Continuous basalt fiber reinforced polypropylene composite material, preparation method and application | |
| CN113265141A (en) | Antimony-free flame-retardant reinforced poly (p-phenylene terephthalamide) composite material, preparation method and application | |
| CN111349335A (en) | Reinforced polyamide 6 composition and preparation method thereof |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210817 |