CN114736242B - Preparation method and application of copolymerized flame retardant, polyamide and preparation method thereof - Google Patents
Preparation method and application of copolymerized flame retardant, polyamide and preparation method thereof Download PDFInfo
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- CN114736242B CN114736242B CN202210581070.5A CN202210581070A CN114736242B CN 114736242 B CN114736242 B CN 114736242B CN 202210581070 A CN202210581070 A CN 202210581070A CN 114736242 B CN114736242 B CN 114736242B
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- 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 116
- 239000003063 flame retardant Substances 0.000 title claims abstract description 113
- 239000004952 Polyamide Substances 0.000 title claims abstract description 74
- 229920002647 polyamide Polymers 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 26
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 33
- 239000003963 antioxidant agent Substances 0.000 claims description 19
- 230000003078 antioxidant effect Effects 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000314 lubricant Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 10
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- -1 pentylene diamine Chemical class 0.000 claims description 6
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 6
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 claims description 5
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 claims description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 229920006021 bio-based polyamide Polymers 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000002464 physical blending Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 description 2
- 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 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a preparation method and application of a copolymerization flame retardant, polyamide and a preparation method thereof. The preparation method of the copolymerization flame retardant comprises the following steps: (1) Reacting pentanediamine with unsaturated dibasic acid to obtain solid salt; (2) Under the protection of inert gas, heating to melt the solid salt and DOPO flame retardant, then reacting under the stirring condition at 140-170 ℃, cooling, and purifying to obtain the copolymerization flame retardant. The flame retardant prepared by the invention can effectively improve the flame retardant property of polyamide, and simultaneously, the obtained polyamide has good mechanical property.
Description
Technical Field
The invention relates to a preparation method and application of a copolymerization flame retardant, and also relates to polyamide and a preparation method thereof.
Background
Polyamide is widely used in various fields such as machining, automobile industry, electronic and electric appliances, textile, etc. because of its excellent mechanical properties, thermal stability, abrasion resistance and chemical corrosion resistance. Most of the high-end application scenes require that the polyamide material has good flame retardant properties. At present, the method for improving the flame retardant property of polyamide in the market is mainly a physical blending modification method. The physical blending method is simple to operate and low in cost, and can achieve a good flame retardant effect, but the method can introduce a large amount of heterogeneous components, so that other properties of the polyamide material are sacrificed. In addition, the flame retardant of the physical blending method is easy to decompose and escape, so that the flame retardant property of the polyamide material can be greatly reduced along with the prolonging of the service time.
The copolymerization flame retardant (reactive flame retardant) is a type of flame retardant capable of participating in polymerization reaction, so that the polymer itself contains a flame retardant component. The existing copolymerization flame retardant has the problems of containing larger steric hindrance groups, lower reaction activity during copolymerization, lower molecular weight of the prepared flame retardant polyamide and the like, and influences other properties (such as mechanical properties) of the flame retardant polyamide. Therefore, there is a need to develop a copolymerized flame retardant capable of improving the flame retardant properties of polyamides while maintaining high mechanical properties.
Polyamides include petroleum-based polyamides and biobased polyamides. Petroleum-based polyamides are prepared by petroleum refining from monomeric diamines or diacids, and with the increasing severity of global environmental forms, the development of petroleum-based polyamides is facing greater environmental pressures. The bio-based polyamide is prepared from the biomass raw material of the pentanediamine, so that not only can the carbon emission be reduced, but also the photosynthesis of plant growth can realize the carbon circulation. Thus, biobased polyamides have great potential for development.
Disclosure of Invention
Accordingly, an object of the present invention is to provide a method for preparing a copolymerized flame retardant, which can effectively improve the flame retardant property of polyamide and simultaneously make the obtained polyamide have good mechanical properties.
Another object of the present invention is to provide a use of the above-mentioned copolymerized flame retardant for improving flame retardant properties of polyamides.
It is a further object of the present invention to provide a polyamide which has good flame retardant properties and mechanical properties.
It is still another object of the present invention to provide a process for producing the above polyamide, which is simple in process, green and low in carbon, and can be directly polycondensed to obtain a bio-based flame retardant polyamide excellent in performance.
The invention adopts the following technical scheme to realize the aim.
In one aspect, the invention provides a method for preparing a copolymerized flame retardant, comprising the following steps:
(1) Reacting pentanediamine (B) with unsaturated dibasic acid to obtain solid salt;
(2) Under the protection of inert gas, heating to melt the solid salt and DOPO flame retardant, then reacting under the stirring condition at 140-170 ℃, cooling, and purifying to obtain the copolymerization flame retardant.
In the present invention, in order to distinguish the raw material of pentamethylenediamine in the different steps, the applicant has noted that the raw material of pentamethylenediamine required in the preparation of the copolymerized flame retardant is pentamethylenediamine (B), and the raw material of pentamethylenediamine required in the preparation of the polyamide is pentamethylenediamine (a).
The invention provides a preparation method of a copolymerization flame retardant, which can effectively improve the flame retardant property of a polyamide material, PO generated during combustion can be quenched with HOH generated during combustion, phosphoric acid as a product can catalyze polyamide to be dehydrated to form carbon, water volatilizes to take away heat, and a uniform and compact carbon layer can be formed to block air, so that the copolymerization flame retardant prepared by the preparation method has a gas phase flame retardant mechanism and a condensed phase flame retardant mechanism.
Compared with DOPO flame retardant (namely 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), traditional DDP flame retardant ([ (6-oxo-6H-dibenzo [ c, e ] [1,2] oxaphospha-hexacyclic-6-yl) methyl ] succinic acid) or DDP flame retardant modified by adopting a traditional method, the invention introduces the pentanediamine in the preparation process of the copolymerization flame retardant, greatly improves the water solubility of the copolymerization flame retardant, and is more beneficial to dispersing in a polymerization system. In addition, the unsaturated dibasic acid is easy to form salt with the pentanediamine, and the carbon-carbon double bond of the unsaturated dibasic acid and the DOPO flame retardant are utilized for addition reaction, so that the reactivity of the copolymerization flame retardant can be greatly improved, and the uniformity of a polymerization product is improved.
In step (1) of the present invention, the reaction temperature may be 30 to 80℃and preferably 50 to 65 ℃. The reaction time may be 1 to 5 hours, preferably 1.5 to 2.5 hours. The temperature of the cooling crystallization may be 0 to 20 ℃, preferably 5 to 10 ℃. Thus, the solid salt with higher yield and purity can be obtained under lower energy consumption.
According to some preferred embodiments of the present invention, the molar ratio of the pentanediamine (B) to the unsaturated dibasic acid is (1-1.1): 1, which helps to save costs and increase the yield of solid salts.
According to one embodiment of the invention, the pentanediamine (B), the unsaturated dibasic acid and the deionized water are mixed to obtain a mixed solution; and (3) reacting the mixed solution at 30-80 ℃ for 1-5 hours, cooling for crystallization after the reaction is finished, filtering, washing and drying to obtain the solid salt.
In certain embodiments, step (1) further comprises adjusting the pH of the mixed liquor to 7.2 to 7.5. According to some embodiments of the invention, the pH of the mixed liquor is adjusted by adding pentanediamine or an unsaturated dibasic acid.
In the present invention, the unsaturated dibasic acid may be selected from unsaturated dibasic acids having less than 6 carbon atoms, preferably one or more of itaconic acid, maleic acid and fumaric acid, more preferably itaconic acid or maleic acid. Thus, the copolymerization flame retardant with higher reactivity is easier to prepare.
In the present invention, the pentylene diamine may be produced from renewable plant materials, for example, by microbial fermentation.
According to the preparation method of the present invention, preferably, the step (1) includes the following specific steps: adding the pentanediamine (B) into the water solution of the unsaturated dibasic acid under the stirring condition to obtain a mixed solution; reacting the mixed solution at 30-80 ℃ for 1-5 h, and then cooling and crystallizing to obtain the solid salt;
wherein the molar ratio of the pentanediamine (B) to the unsaturated dibasic acid is (1-1.2): 1;
the unsaturated dibasic acid is selected from one or more of itaconic acid, maleic acid and fumaric acid.
In the step (2) of the present invention, the mass ratio of the solid salt to the DOPO flame retardant may be (0.8 to 1.2): 1, preferably (1 to 1.1): 1. The reaction temperature may be 140 to 170 ℃, preferably 155 to 170 ℃, for example 160 ℃. The reaction time may be 1 to 5 hours, preferably 2.5 to 3.5 hours. The temperature of cooling is not particularly limited as long as crystallization is possible, and for example, cooling to 60℃or lower is possible. Purification may include recrystallization. In certain embodiments, the purification process is: recrystallizing with acetone as solvent, filtering, washing and drying. This can improve the flame retardant properties of the polyamide material.
In the present invention, the "inert gas" may be one or more of nitrogen, argon or helium, preferably nitrogen, argon or helium, more preferably nitrogen.
In the present invention, the washing may be performed by water washing or alcohol washing, preferably alcohol washing, and more preferably ethanol washing. The unsaturated dibasic acid and the pentanediamine can be better washed by adopting absolute ethyl alcohol for washing, and the product with higher purity is obtained.
According to the preparation method of the present invention, preferably, in the step (2), the mass ratio of the solid salt to the DOPO flame retardant is (0.8-1.2): 1; the cooling temperature is less than or equal to 60 ℃; the purification process comprises the following steps: the recrystallization was performed using acetone as a solvent.
On the other hand, the invention also provides the application of the copolymerization flame retardant prepared by the preparation method in improving the flame retardant property of polyamide.
In a further aspect, the present invention provides a polyamide prepared from a starting material comprising a copolymerized flame retardant prepared according to the preparation method described above.
The polyamide according to the invention preferably has a structure represented by formula (I) ：
Wherein a is an integer from 4 to 16; x and y are each independently selected from integers from 1 to 50.
According to some embodiments of the invention, a is 4, 8, 9, 10 or 11; x and y are each independently selected from integers from 1 to 50.
In yet another aspect, the present invention provides a method for preparing a polyamide, comprising the steps of:
the preparation method comprises the steps of (1) carrying out polymerization reaction on pentanediamine (A), long carbon chain dibasic acid, a catalyst, an antioxidant and a copolymerization flame retardant prepared according to the preparation method under the condition of temperature programming to obtain polyamide;
wherein the long carbon chain diacid is selected from one or more of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and tridecanedioic acid;
wherein the catalyst is selected from one or more of sodium hypophosphite monohydrate, disodium hydrogen phosphate, sodium hypophosphite, phosphoric acid and hypophosphorous acid;
wherein the antioxidant is one or more selected from antioxidant 1010, antioxidant 1098, antioxidant 168, antioxidant 626 and antioxidant SEED;
wherein the mass ratio of the pentylene diamine (A) to the copolymerized flame retardant is (2-9.5): 1.
In the present invention, the long carbon chain dibasic acid may be selected from one or more of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, preferably adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid or tridecanedioic acid. The catalyst may be selected from one or more of sodium hypophosphite monohydrate, disodium hydrogen phosphate, sodium hypophosphite, phosphoric acid and hypophosphorous acid, and is preferably a composite catalyst consisting of sodium hypophosphite monohydrate, phosphoric acid and disodium hydrogen phosphate. The antioxidant may be one or more selected from antioxidant 1010, antioxidant 1098, antioxidant 168, antioxidant 626, antioxidant SEED, preferably antioxidant 1010 and/or antioxidant SEED.
In certain embodiments, the feedstock for making the polyamide further comprises a lubricant. The lubricant may be selected from one or more of silicone oil, white oil, liquid paraffin, preferably silicone oil, white oil or liquid paraffin.
In the present invention, the mass ratio of the pentylene diamine (A) to the copolymerized flame retardant is (2 to 9.5): 1, preferably (3.5 to 7.5): 1, and more preferably (4 to 7): 1. Thus, the flame retardant property of the polyamide can be effectively improved, and the good mechanical property of the polyamide is ensured.
According to the preparation method of the present invention, preferably, the mass ratio of the pentylene diamine (A) to the copolymerized flame retardant is (3.5-7.5): 1.
According to the preparation method of the present invention, preferably, 35 to 75 parts by weight of pentylene diamine (A), 90 to 110 parts by weight of long carbon chain dibasic acid, 0.25 to 0.55 part by weight of catalyst, 0.3 to 0.7 part by weight of antioxidant, 0.1 to 0.3 part by weight of lubricant and 8 to 16 parts by weight of the copolymerized flame retardant are used.
According to some preferred embodiments of the invention, the polyamide is prepared from the following raw materials: 40 to 75 weight portions of pentanediamine (A), 95 to 105 weight portions of long carbon chain dibasic acid, 0.35 to 0.55 weight portion of catalyst, 0.3 to 0.5 weight portion of antioxidant, 0.1 to 0.2 weight portion of lubricant and 9 to 15.5 weight portions of copolymerization flame retardant. The polyamide thus produced has both good flame retardant and mechanical properties.
According to the production method of the present invention, preferably, the temperature-programmed conditions are as follows:
heating to 50-80 ℃, and then reacting for 0.5-3 h at a constant temperature of 50-80 ℃;
heating from 50-80 ℃ to 120-150 ℃ and then reacting for 0.5-3 h at 120-150 ℃;
heating from 120-150 ℃ to 190-210 ℃, and then reacting for 1-5 h at 190-210 ℃ and 1.2-1.8 MPa;
heating and exhausting for 1-2 h, heating from 190-210 ℃ to 220-230 ℃, exhausting until the pressure is reduced to below 0.3 Mpa;
heating from 220-230 ℃ to 240-260 ℃, keeping the temperature at 240-260 ℃, vacuumizing to-0.06 to-0.09 MPa, and continuing the reaction for 10-60 min.
According to some preferred embodiments of the invention, the temperature programmed conditions are as follows:
heating to 60-80 ℃, and then reacting for 0.5-1.5 h at the constant temperature of 60-80 ℃;
heating from 60-80 ℃ to 130-150 ℃ and then reacting for 0.5-1.5 h at 130-150 ℃;
heating from 130-150 ℃ to 190-210 ℃, and then reacting for 1.5-3 h at 190-210 ℃ and 1.2-1.8 MPa;
heating and exhausting for 1-2 h, heating from 190-210 ℃ to 220-230 ℃, exhausting to 0.09-0.15 Mpa;
heating from 220-230 ℃ to 240-260 ℃, keeping the temperature at 240-260 ℃, vacuumizing to-0.06 to-0.09 MPa, and continuing the reaction for 10-30 min. Therefore, time and cost can be saved, production efficiency is improved, uniform forward movement can be guaranteed through strictly controlling temperature rise and exhaust rate, and polyamide with better molecular weight and better mechanical property can be obtained.
The copolymerization flame retardant prepared by the preparation method can effectively improve the flame retardant property of polyamide and simultaneously maintain the good mechanical property of the polyamide. The polyamide of the invention has good flame retardant property and mechanical property. The preparation method of the polyamide has the advantages of simple process, green and low carbon, and can directly obtain the bio-based flame-retardant polyamide with excellent performance through polycondensation.
Detailed Description
The present invention will be further described with reference to the following specific embodiments, but the scope of the present invention is not limited thereto.
The test method is described as follows:
(1) Testing of thermodynamic properties:
and measuring the melting point of the sample by adopting a TAQ2000 differential scanning calorimeter, wherein the temperature rising rate is 10 ℃/min and the temperature ranges from 30 ℃ to 300 ℃ under the nitrogen atmosphere.
And (3) measuring the thermal decomposition temperature of the sample in the nitrogen atmosphere by adopting a TAQ50 thermogravimetric analyzer, wherein the temperature rising rate is 10 ℃/min, and the temperature range is 50-700 ℃.
(2) Testing of mechanical properties:
the tensile and bending properties of the different bars were measured using an Instron 5567 universal tester, wherein the tensile rate was set at 10mm/min and the temperature was 25 ℃; the pressing rate of bending was 2mm/min, the span was 64mm, the bending deflection was 6% and the temperature was 25 ℃.
(3) Testing of flame retardant properties:
the limit oxygen index tester of HC-2CZ is adopted to test the limit oxygen index at room temperature by referring to the standard of GB/T2406.2-2009 "oxygen index method for determining combustion behavior of plastics". Spline specification: 80 mm. Times.10 mm. Times.4 mm.
The prepared bars were tested for vertical burn performance with reference to GB/T2408-2008 standards for determination of horizontal and vertical methods for burn Performance of plastics. Spline specification: 130 mm. Times.13 mm. Times.3.0 mm.
In the process of testing mechanical properties and flame retardant properties, test bars used were prepared according to GB/T9352-2008 compression molding of Plastic thermoplastic Material samples. The specific process comprises the following steps: firstly, the prepared bio-based flame retardant polyamide is dried for 3 hours in vacuum at the temperature of 100 ℃, then a WZS10 type injection molding machine is adopted to mold sample bars, the temperature of a charging barrel is set to be 20 ℃ above the melting point, the mold temperature is 60 ℃, and the injection molding pressure is 7MPa.
In the preparation examples, examples and comparative examples of the present invention, unless otherwise specified, parts are by weight.
In the following examples and comparative examples, sodium hypophosphite monohydrate and disodium hydrogen phosphate 2:1 mixed catalyst were used as the catalysts unless otherwise specified; the lubricant is silicone oil 523.
Preparation example 1
(1) 100 parts of itaconic acid is dissolved in 100 parts of deionized water, 78.54 parts of pentanediamine (B) is added, and the mixture is uniformly mixed to obtain a mixed solution;
the pH of the mixed solution is adjusted to 7.2 by adding itaconic acid, then the mixed solution is reacted for 2 hours at the temperature of 60 ℃ under stirring, and after the reaction is finished, the mixed solution is cooled and crystallized at the temperature of 6 ℃, is filtered by suction, is washed by ethanol, and is dried to obtain white solid salt.
(2) Adding 107.5 parts of solid salt and 100 parts of DOPO in the step (1) into a three-neck flask, heating to 160 ℃ under the protection of nitrogen, reacting for 3 hours under the stirring condition and 160 ℃, cooling to below 60 ℃, adding 100 parts of acetone for dissolving, recrystallizing, and carrying out suction filtration, washing and drying to obtain the copolymerization flame retardant.
Preparation example 2
(1) Dissolving 105 parts of maleic acid in 100 parts of deionized water, then adding 78.54 parts of pentanediamine (B), and uniformly mixing to obtain a mixed solution;
the pH of the mixed solution is adjusted to 7.2 by adding maleic acid, then the mixed solution is reacted for 2 hours at the temperature of 60 ℃ under stirring, and after the reaction is finished, the mixed solution is cooled and crystallized at the temperature of 6 ℃, is filtered by suction and is washed by ethanol, and is dried to obtain white solid salt.
(2) Adding 110 parts of solid salt in the step (1) and 100 parts of DOPO into a three-neck flask, heating to 160 ℃ under the protection of nitrogen, reacting for 3 hours under the stirring condition and 170 ℃, cooling to below 60 ℃, adding 100 parts of acetone for dissolution, recrystallizing, and carrying out suction filtration, washing and drying to obtain the copolymerization flame retardant.
Example 1
71.32 parts of pentanediamine (A), 100 parts of adipic acid, 10.94 parts of copolymerized flame retardant (prepared in preparation example 1), 0.55 part of antioxidant SEED, 0.36 part of catalyst, 100 parts of water and 0.18 part of lubricant are weighed out;
placing the raw materials into a reaction kettle, repeatedly replacing air in the kettle with nitrogen for 3 times, then filling nitrogen until the pressure in the kettle is 0.090MPa, starting stirring, and setting the stirring speed to be 100rpm;
finally, the temperature programming is carried out, and the specific steps are as follows:
1) Heating to 60 ℃, and reacting for 1h at the constant temperature of 60 ℃;
2) Then heating to 150 ℃, and reacting for 1h at the constant temperature of 150 ℃;
3) Continuously heating to 210 ℃ to perform a prepolymerization reaction, and reacting for 2 hours at 210 ℃ and 1.7 MPa;
4) Heating and exhausting for 1.5h, heating from 210 ℃ to 230 ℃, and reducing the pressure to normal pressure;
5) Continuously heating to 260 ℃, vacuumizing until the pressure in the kettle reaches minus 0.08MPa, and continuously reacting for 10min;
6) Finally, nitrogen is filled into the reaction kettle, so that the pressure in the kettle is restored to normal pressure, and the polyamide is obtained through cooling, discharging, granulating and vacuum drying at 90 ℃.
The properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Example 2
50.52 parts of pentanediamine (A), 100 parts of sebacic acid, 9.61 parts of copolymerized flame retardant (prepared in preparation example 1), 0.48 part of antioxidant SEED, 0.32 part of catalyst, 100 parts of water and 0.16 part of lubricant are weighed;
placing the raw materials into a reaction kettle, repeatedly replacing air in the kettle with nitrogen for 3 times, then filling nitrogen until the pressure in the kettle is 0.090MPa, starting stirring, and setting the stirring speed to be 100rpm;
finally, the temperature programming is carried out, and the specific steps are as follows:
1) Heating to 80 ℃, and reacting for 1h at the constant temperature of 80 ℃;
2) Then heating to 150 ℃, and reacting for 1h at the constant temperature of 150 ℃;
3) Continuously heating to 190 ℃ to perform a prepolymerization reaction, and reacting for 2 hours at 190 ℃ and 1.5 MPa;
4) Heating and exhausting for 1.5h, heating from 190 ℃ to 230 ℃, and reducing the pressure to normal pressure;
5) Continuously heating to 240 ℃, vacuumizing until the pressure in the kettle reaches minus 0.08MPa, and continuously reacting for 10min;
6) Finally, nitrogen is filled into the reaction kettle, so that the pressure in the kettle is restored to normal pressure, and the polyamide is obtained through cooling, discharging, granulating and vacuum drying at 90 ℃.
The properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Example 3
The procedure of example 1 was repeated except that the raw materials used were different: in this embodiment, the raw materials used are: 47.25 parts of pentanediamine (A), 100 parts of undecanedioic acid, 9.4 parts of copolymerized flame retardant (prepared in preparation example 1), 0.47 part of antioxidant SEED, 0.31 part of catalyst, 100 parts of water and 0.16 part of lubricant. The properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Example 4
The procedure of example 1 was repeated except that the raw materials used were different: in this embodiment, the raw materials used are: 44.37 parts of pentanediamine (A), 100 parts of dodecanedioic acid, 9.22 parts of a copolymerized flame retardant (prepared in preparation example 1), 0.46 part of an antioxidant SEED, 0.31 part of a catalyst, 100 parts of water and 0.15 part of a lubricant. The properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Example 5
The procedure of example 1 was repeated except that the raw materials used were different: in this embodiment, the raw materials used are: 41.87 parts of pentanediamine (A), 100 parts of tridecanedioic acid, 9.22 parts of copolymerized flame retardant (prepared by preparation example 1), 0.45 part of antioxidant SEED, 0.31 part of catalyst, 100 parts of water and 0.15 part of lubricant. The properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Example 6
The procedure of example 1 was followed, except that the amount of copolymerized flame retardant used was varied: in this example, the amount of copolymerized flame retardant was 14.90 parts. The properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Comparative example 1
The procedure of example 1 was repeated except that the copolymerized flame retardant was not added. The properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Comparative example 2
The procedure of example 2 was repeated except that the copolymerized flame retardant was not added. The properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Comparative example 3
The procedure of example 3 was repeated except that the copolymerized flame retardant was not added. The properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Comparative example 4
The procedure of example 4 was repeated except that the copolymerized flame retardant was not added. The properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Comparative example 5
The procedure of example 5 was repeated except that the copolymerized flame retardant was not added. The properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Comparative example 6
The procedure of example 1 was repeated except that the copolymerized flame retardant was replaced with flame retardant DOPO. The properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Comparative example 7
The procedure of example 1 was repeated except that the copolymerized flame retardant was replaced with a flame retardant DDP: the properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Comparative example 8
The procedure of example 1 was repeated except that the copolymerized flame retardant was replaced with the modified flame retardant DDP. In this comparative example, the modified flame retardant DDP was prepared as follows: dispersing 100 parts of DDP flame retardant into 200 parts of absolute ethyl alcohol, gradually dropwise adding 29.51 parts of pentanediamine (B) under the stirring condition, then reacting for 3 hours at 60 ℃, and carrying out suction filtration, washing and drying to obtain the modified flame retardant DDP prepared in the traditional mode. The properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Comparative example 9
The procedure of example 1 was followed, except that the amount of copolymerized flame retardant used was varied: in this comparative example, the amount of the copolymerized flame retardant was 3.5 parts. The properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Comparative example 10
The procedure of example 1 was followed, except that the amount of copolymerized flame retardant used was varied: in this comparative example, the amount of the copolymerized flame retardant was 7.14 parts. The properties of the obtained polyamide were measured, and the test results are shown in Table 1.
Table 1 shows a list of the performance parameters of the polyamides obtained
It can be seen from Table 1 that the flame retardant properties of the resulting polyamide can be significantly improved by using the copolymerized flame retardant of the present invention while maintaining high mechanical properties. As can be seen from example 1 and comparative examples 6 to 8, flame retardant DOPO, flame retardant DDP and flame retardant DDP modified by conventional methods can also cause a significant decrease in mechanical properties of polyamide materials while improving flame retardant properties of the polyamide materials. The copolymerized flame retardant has less influence on the mechanical properties of polyamide. The comprehensive properties (including mechanical properties and flame retardant properties) of the polyamide prepared by the copolymerization flame retardant are obviously superior to those of the polyamide prepared by flame retardant DOPO, flame retardant DDP and flame retardant DDP modified by the traditional method.
In addition, it can be seen from examples 1, 6 and comparative examples 9 to 10 that the polyamide produced by the production method of the present invention can have both good flame retardant properties and mechanical properties.
The present invention is not limited to the above-described embodiments, and any modifications, improvements, substitutions, and the like, which may occur to those skilled in the art, fall within the scope of the present invention without departing from the spirit of the invention.
Claims (3)
1. A process for producing a polyamide, characterized in that,
the polyamide has a structure represented by formula (I):
（I），
wherein a is an integer from 4 to 11; x and y are each independently selected from integers from 1 to 50;
the preparation method comprises the following steps:
performing polymerization reaction on pentanediamine (A), long carbon chain dibasic acid, catalyst, antioxidant, lubricant and copolymerization flame retardant under the condition of programmed temperature rise to obtain polyamide;
wherein, the temperature programming conditions are as follows:
heating to 50-80 ℃, and then reacting for 0.5-3 h at a constant temperature of 50-80 ℃;
heating from 50-80 ℃ to 120-150 ℃ and then reacting for 0.5-3 h at 120-150 ℃;
heating from 120-150 ℃ to 190-210 ℃, and then reacting for 1-5 h at 190-210 ℃ and 1.2-1.8 MPa;
heating and exhausting for 1-2 h, heating from 190-210 ℃ to 220-230 ℃, exhausting until the pressure is reduced to below 0.3 Mpa;
raising the temperature from 220-230 ℃ to 240-260 ℃, keeping the temperature at 240-260 ℃, vacuumizing to-0.06 to-0.09 MPa, and continuing to react for 10-60 min;
wherein the long carbon chain diacid is selected from one or more of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and tridecanedioic acid;
wherein the catalyst is a composite catalyst consisting of sodium hypophosphite monohydrate and disodium hydrogen phosphate;
wherein the antioxidant is selected from one or more of antioxidant 1010 and antioxidant SEED;
wherein, 35 to 75 weight parts of pentanediamine (A), 90 to 110 weight parts of long carbon chain dibasic acid, 0.25 to 0.55 weight parts of catalyst, 0.3 to 0.7 weight parts of antioxidant, 0.1 to 0.3 weight parts of lubricant and 8 to 16 weight parts of copolymerization flame retardant;
wherein the mass ratio of the pentanediamine (A) to the copolymerization flame retardant is (2-9.5): 1;
the preparation method of the copolymerization flame retardant comprises the following steps:
(1) Under the stirring condition, adding the pentanediamine (B) into the water solution of the unsaturated dibasic acid to obtain a mixed solution; reacting the mixed solution at 30-80 ℃ for 1-5 h, and then cooling and crystallizing to obtain solid salt;
wherein the molar ratio of the pentanediamine (B) to the unsaturated dibasic acid is (1-1.2): 1;
the unsaturated dibasic acid is selected from one of itaconic acid and maleic acid;
(2) Under the protection of inert gas, heating to melt the solid salt and DOPO flame retardant, then reacting under the stirring condition at 140-170 ℃, cooling, and purifying to obtain the copolymerization flame retardant.
2. The process according to claim 1, wherein the mass ratio of the pentylene diamine (A) to the copolymerized flame retardant is (3.5-7.5): 1.
3. The method according to claim 1, wherein in the step (2) of the method for producing a copolymerized flame retardant, the mass ratio of the solid salt to the DOPO flame retardant is (0.8-1.2): 1;
the cooling temperature is less than or equal to 60 ℃;
the purification process comprises the following steps: the recrystallization was performed using acetone as a solvent.
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