CN114539313A - Double-reaction type phosphonate cross-linking flame retardant and preparation method thereof - Google Patents
Double-reaction type phosphonate cross-linking flame retardant and preparation method thereof Download PDFInfo
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- CN114539313A CN114539313A CN202210168726.0A CN202210168726A CN114539313A CN 114539313 A CN114539313 A CN 114539313A CN 202210168726 A CN202210168726 A CN 202210168726A CN 114539313 A CN114539313 A CN 114539313A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 89
- 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 80
- 238000004132 cross linking Methods 0.000 title claims abstract description 30
- 238000006757 chemical reactions by type Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 title claims abstract description 13
- -1 phosphonate compound Chemical class 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229910001868 water Inorganic materials 0.000 claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- WUEAMTVQNGYLRI-UHFFFAOYSA-N 2-dichlorophosphoryl-1,3,5-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC(C(C)C)=C(P(Cl)(Cl)=O)C(C(C)C)=C1 WUEAMTVQNGYLRI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000004042 decolorization Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000004821 distillation Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 24
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 17
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 claims description 4
- SCLFRABIDYGTAZ-UHFFFAOYSA-N methylphosphonic acid dichloride Chemical compound CP(Cl)(Cl)=O SCLFRABIDYGTAZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 3
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 3
- SHDZTIZBSYDZSH-UHFFFAOYSA-N 2-methylprop-2-enoyl bromide Chemical compound CC(=C)C(Br)=O SHDZTIZBSYDZSH-UHFFFAOYSA-N 0.000 claims description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 2
- VWQXLMJSFGLQIT-UHFFFAOYSA-N prop-2-enoyl bromide Chemical compound BrC(=O)C=C VWQXLMJSFGLQIT-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- ODKNOOMYXHAPGC-UHFFFAOYSA-N 1-dichlorophosphoryl-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(C(=C(C(=C1P(=O)(Cl)Cl)F)F)F)F ODKNOOMYXHAPGC-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 21
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract description 16
- 239000004926 polymethyl methacrylate Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000178 monomer Substances 0.000 abstract description 4
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 33
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 24
- 239000007788 liquid Substances 0.000 description 24
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 21
- 239000007789 gas Substances 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 12
- 239000011780 sodium chloride Substances 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000003788 bath preparation Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- WCRZYCXJFFOULB-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)phosphonic acid Chemical compound OP(O)(=O)C1=C(F)C(F)=C(F)C(F)=C1F WCRZYCXJFFOULB-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 125000005499 phosphonyl group Chemical group 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- GHKOKZCLVBPWLG-UHFFFAOYSA-N FC1=C(C(=C(C(=C1OP(O)=O)F)F)F)F Chemical compound FC1=C(C(=C(C(=C1OP(O)=O)F)F)F)F GHKOKZCLVBPWLG-UHFFFAOYSA-N 0.000 description 3
- AAOHKRNFHQXDFX-UHFFFAOYSA-N [4-[1,1,1,3,3,3-hexafluoro-2-[4-(2-methylprop-2-enoyloxy)phenyl]propan-2-yl]phenyl] 2-methylprop-2-enoate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(OC(=O)C(C)=C)C=C1 AAOHKRNFHQXDFX-UHFFFAOYSA-N 0.000 description 3
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- LFINSDKRYHNMRB-UHFFFAOYSA-N diazanium;oxido sulfate Chemical compound [NH4+].[NH4+].[O-]OS([O-])(=O)=O LFINSDKRYHNMRB-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- QLZHNIAADXEJJP-UHFFFAOYSA-L dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-L 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- ZSVFYHKZQNDJEV-UHFFFAOYSA-N (2,3,4-tribromophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(Br)C(Br)=C1Br ZSVFYHKZQNDJEV-UHFFFAOYSA-N 0.000 description 1
- BUPRYTFTHBNSBD-UHFFFAOYSA-N (2,3,4-tribromophenyl) prop-2-enoate Chemical compound BrC1=CC=C(OC(=O)C=C)C(Br)=C1Br BUPRYTFTHBNSBD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
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)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a dual-reaction phosphonate cross-linking flame retardant and a preparation method thereof, and the method comprises the following steps: reacting organic phosphonic dichloride and an excessive dihydroxy compound under the conditions of a solvent and a Lewis acid catalyst to obtain a hydroxyl-containing phosphonate compound; and cooling the hydroxyl-containing phosphonate compound to 0-7 ℃, slowly dropwise adding acryloyl halide, and performing suction filtration, alkali washing, water washing, separation, color removal and distillation to obtain the double-reaction phosphonate cross-linked flame retardant. The double-reaction type phosphonate cross-linking flame retardant is added into PMMA as a reaction type flame retardant, not only has a flame retardant effect, but also can be used as a cross-linking agent of a reaction monomer, the performance of a PMMA material cannot be influenced, the transparency of the prepared PMMA material is good, and the flame retardant prepared by the method has the advantages of high yield, simple process, low cost and suitability for large-scale production.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a dual-reaction type phosphonate cross-linked flame retardant and a preparation method thereof.
Background
To avoid spontaneous ignition or thermal combustion of the organic material, a certain amount of flame retardant is usually added to the organic material. The flame retardant is divided into an additive type and a reactive type: the additive type is a micromolecular substance, the addition amount is usually 10-40%, the dosage is relatively large, the mechanical property or the optical property of the material can be influenced, the additive type is combined with the main material by adsorption, and the mechanical property of the material can be influenced due to the fact that the additive type is not uniformly distributed in the main material; the reactive type contains unsaturated double bonds, is combined with the main material by the bond bonds through polymerization reaction, is integrated with the main material, is relatively uniformly distributed, and does not influence the mechanical property of the material. The reactive flame retardant has the advantages that: can be used as polymer molecular monomer and can resist flame. Compared with additive flame retardants, reactive flame retardants are especially important in the future of high-tech materials.
Currently, reactive flame retardants are limited to partially brominated flame retardants such as tribromophenyl acrylate or tribromophenyl methacrylate, others of which are rarely reactive. Although the bromine flame retardant is a classic flame retardant and is internationally recognized, yellow bromine released by combustion of the bromine flame retardant is extremely toxic, so that the application of the bromine flame retardant is gradually inclined to the phosphorus flame retardant. Phosphorus flame retardants are used in ever increasing amounts due to their low toxicity. However, most of the phosphorus flame retardants are small molecules or small molecular weight polymers, and reactive phosphorus flame retardants are rarely found. Particularly in PMMA materials, the flame retardant often influences the transparency of the materials, most of the flame retardant is not suitable for PMMA materials, so that the flame retardant is rarely added into the PMMA materials, and the use of the PMMA materials added with the flame retardant is greatly expanded. Most of PMMA materials added with flame retardant are added with low molecular weight phosphate ester polymers. In actual production, a proper dual-reaction phosphonate cross-linking flame retardant is urgently needed when a PMMA material with high strength and high transparency is prepared, and the flame retardant is a cross-linking agent of a reaction monomer and can play a flame-retardant role in integrally improving the material property.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a dual-reaction phosphonate cross-linking flame retardant and a preparation method thereof.
The invention provides a preparation method of a dual-reaction type phosphonate ester cross-linking flame retardant, which comprises the following steps:
(1) reacting organic phosphonic dichloride and an excessive dihydroxy compound under the conditions of a solvent and a Lewis acid catalyst to obtain a hydroxyl-containing phosphonate compound;
(2) and cooling the hydroxyl-containing phosphonate compound to 0-7 ℃, slowly dropwise adding acryloyl halide, reacting at the constant temperature of 30-50 ℃ for 1.5-2.5 h, and performing suction filtration, alkali washing, water washing, separation, color removal and distillation to obtain the double-reaction type phosphonate cross-linking flame retardant.
Further, the organic phosphonyl dichloride in the step (1) is one of methyl phosphonyl dichloride, phenyl phosphonyl dichloride and pentafluorophenyl phosphonyl dichloride, and the dihydroxy compound is bisphenol A or hexafluorobisphenol A.
Further, the solvent in the step (1) is one of benzene, toluene and xylene, and the lewis acid catalyst is one of anhydrous aluminum trichloride, anhydrous magnesium bromide, anhydrous magnesium chloride and anhydrous zinc chloride.
Further, the reaction temperature in the step (1) is 140-160 ℃, and the reaction time is 7-9 hours.
Further, in the step (1), the molar ratio of the organic phosphonyl dichloride and the dihydroxy compound is 1: 2.5-5.0, the mass ratio of the total mass of the organic phosphonyl dichloride and the dihydroxy compound to the solvent is 100: 250-500, and the mass ratio of the total mass of the organic phosphonyl dichloride and the dihydroxy compound to the Lewis acid catalyst is 100: 1.0-5.0.
Further, tail gas generated in the reaction process is collected in the steps (1) and (2) and reacts with the sodium hydroxide solution to generate sodium halide and water.
Further, the acryloyl halide in the step (2) is one of acryloyl chloride, acryloyl bromide, methacryloyl chloride or methacryloyl bromide.
Further, the molar ratio of the hydroxyl-containing phosphonate compound to the acryloyl halide in the step (2) is 1: 2.5-5.0.
Further, in the step (2), alkali washing is performed by using a 2-8% potassium carbonate aqueous solution, and the column is leached by using activated carbon for color removal.
The invention also provides a double-reaction type phosphonate ester cross-linking flame retardant prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
the double-reaction type phosphonate ester cross-linking flame retardant is added into PMMA as a reaction type flame retardant, not only has a flame retardant effect, but also can be used as a cross-linking agent of a reaction monomer, the performance of a PMMA material cannot be influenced, the transparency of the prepared PMMA material is good, the prepared PMMA material is a brand new phosphine flame retardant variety, and the flame retardant prepared by the method is high in yield, simple in process, low in cost and suitable for large-scale production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
The flame retardant of this example is bis (4' -bisphenol a methacrylate) methylphosphonate, and the specific preparation method is as follows:
(1) adding 83.8g of bisphenol A, 4.0g of anhydrous aluminum trichloride and 250g of toluene into a 500mL reactor, introducing nitrogen, introducing tail gas into a sodium hydroxide solution sealer with the concentration of 40%, adjusting the temperature to 140 ℃, slowly dropwise adding 16.2g of methylphosphonic dichloride under the stirring condition, setting the dropwise adding time to be 6 hours, adjusting the temperature to 160 ℃ after the dropwise adding is finished, and continuing to react for 2 hours. Carrying hydrogen chloride gas generated in the reaction process into a sodium hydroxide solution sealer by nitrogen, reacting to generate sodium chloride and water, and fully reacting for 8 hours to obtain a hydroxyl-containing methylphosphonic acid bisphenol A ester compound;
(2) after the temperature of the hydroxyl-containing methylphosphonic acid bisphenol A ester compound is reduced to 0 ℃, under the condition of ice bath preparation, 32.0g of methacryloyl chloride is slowly dripped, hydrogen chloride gas generated in the reaction process is carried into a sodium hydroxide solution sealer by nitrogen, sodium chloride and water are generated by reaction, and the dripping time is set to be 4 hours. After the dripping is finished, the reaction is continued for 2 hours at the constant temperature of 40 ℃, unreacted methacryloyl chloride is removed under reduced pressure at the temperature of 50 ℃, then, solid catalyst in the liquid is removed by suction filtration, 4 percent potassium carbonate aqueous solution is used for washing until the liquid is alkaline, then, deionized water is used for washing until the liquid is neutral, the extracted oily liquid enters an activated carbon decoloring filter column to remove yellow substances, toluene and a small amount of water are removed by rotary evaporation at the temperature of 55 ℃, and 121.1g of viscous colorless liquid containing 77.0g of methylphosphonic acid di (4' -bisphenol A methacrylate) and 44.1g of bisphenol A dimethacrylate can be directly used as a cross-linking flame retardant or used for separation.
The yield of the flame retardant prepared in this example was 96.5%, the acid value was 0.020mgKOH/g, the molecular weight was 652.69, and the product was stored at low temperature.
Example 2
The flame retardant of this example is bis (4' -bisphenol a methacrylate) phenylphosphonate, and the specific preparation method is as follows:
(1) in a 500mL reactor, 77.8g of bisphenol A, 4.5g of anhydrous magnesium chloride, 275g of benzene were added, nitrogen gas was introduced, and the tail gas was introduced into a 40% sodium hydroxide solution sealed vessel, the temperature was adjusted to 140 ℃, stirring was turned on, and 22.2g of phenylphosphonyl dichloride was slowly added dropwise over a period of 6 hours. After the dripping is finished, adjusting the temperature to 160 ℃, continuing the reaction for 2 hours, carrying hydrogen chloride gas generated in the reaction process into a sodium hydroxide solution sealer by nitrogen, reacting to generate sodium chloride and water, and fully reacting for 8 hours to obtain a phenyl phosphonic acid bisphenol A ester compound containing hydroxyl;
(2) after the temperature of the phenylphosphonic acid biphenol A ester compound containing hydroxyl is reduced to 5 ℃, slowly dripping 30.2g of methacryloyl chloride under the condition of ice bath preparation, carrying hydrogen chloride gas generated in the reaction process into a sodium hydroxide solution sealer by nitrogen, and reacting to generate sodium chloride and water, wherein the dripping time is set to be 4 hours. After the dripping is finished, the reaction is continued for 2 hours at the constant temperature of 45 ℃, unreacted methacryloyl chloride is removed under reduced pressure at the temperature of 50 ℃, then the solid catalyst in the liquid is removed by suction filtration, 5 percent potassium carbonate aqueous solution is used for washing until the solution is slightly alkaline, and then deionized water is used for washing until the solution is neutral. The extracted oily liquid enters an activated carbon decoloration filter column to remove yellow substances, benzene and a small amount of water are removed by rotary evaporation at 45 ℃ to obtain 118.4g of viscous colorless liquid, 77.8g of phenyl phosphonic acid di (4' -bisphenol A methacrylate) and 40.6g of bisphenol A dimethacrylate, and the viscous colorless liquid can be directly used as a crosslinking flame retardant or used for separation.
The yield of the flame retardant prepared in this example was 95.8%, the acid value was 0.018mgKOH/g, the molecular weight was 714.76, and the product was stored at low temperature.
Example 3
The flame retardant of this example is bis (4' -bisphenol a methacrylate) pentafluorophenyl phosphonate, which is specifically prepared by the following steps:
(1) in a 500mL reactor, 70.6g of bisphenol A, 3.5g of anhydrous zinc chloride and 325g of xylene were added, nitrogen gas was introduced, and the tail gas was introduced into a 40% sodium hydroxide solution sealed vessel, the temperature was adjusted to 140 ℃, stirring was turned on, and 29.4g of pentafluorophenylphosphonodichloride was slowly added dropwise over a period of 6 hours. After the dropwise addition, adjusting the temperature to 160 ℃, continuing the reaction for 3 hours, carrying hydrogen chloride gas generated in the reaction process into a sodium hydroxide solution sealer by nitrogen, reacting to generate sodium chloride and water, and fully reacting for 9 hours to obtain a hydroxyl-containing pentafluorophenyl phosphonic acid bisphenol A ester compound;
(2) after the temperature of the hydroxyl-containing pentafluorophenyl phosphonic acid bisphenol A ester compound is reduced to 7 ℃, under the condition of ice bath preparation, 26.9g of methacrylic acid chloride is slowly dripped, hydrogen chloride gas generated in the reaction process is carried into a sodium hydroxide solution sealer by nitrogen to react to generate sodium chloride and water, the dripping time is set to 4 hours, after the dripping is finished, the reaction is continued for 1.5 hours at the constant temperature of 50 ℃, and unreacted methacrylic acid chloride is removed under reduced pressure at the temperature of 50 ℃. Then, the solid catalyst in the liquid is removed by suction filtration, and the liquid is washed to be alkaline by 5 percent potassium carbonate aqueous solution and then washed to be neutral by deionized water. The extracted oily liquid enters an activated carbon decoloration filter column to remove yellow substances, xylene and a small amount of water are removed by rotary evaporation at 60 ℃, and 123.1g of viscous colorless liquid containing 86.0g of pentafluorophenyl phosphonic acid di (4' -bisphenol A methacrylate) and 37.1g of bisphenol A dimethacrylate can be directly used as a crosslinking flame retardant or used for separation.
The yield of the flame retardant prepared in this example was 95.1%, the acid value was 0.021mgKOH/g, the molecular weight was 834.72, and the product was stored at low temperature.
Example 4
The flame retardant of this example is bis (4' -hexafluorobisphenol a methacrylate) methylphosphonate, and the specific preparation method is as follows:
(1) in a 500mL reactor, 88.4g of hexafluorobisphenol A, 4.0g of anhydrous magnesium bromide and 250g of toluene were added, nitrogen gas was introduced, and the tail gas was introduced into a 40% sodium hydroxide solution sealed vessel, the temperature was adjusted to 140 ℃, stirring was turned on, and 11.6g of methylphosphonyl dichloride was slowly added dropwise with the addition time set to 6 hours. After the dripping is finished, adjusting the temperature to 160 ℃, continuously reacting for 2 hours, carrying hydrogen chloride gas generated in the reaction process into a sodium hydroxide solution sealer by nitrogen, reacting to generate sodium chloride and water, and fully reacting for 8 hours to obtain a hydroxyl-containing bis (hexafluorobisphenol A) methylphosphonate compound;
(2) cooling the hydroxyl-containing methyl phosphonic acid bis (hexafluorobisphenol A) ester compound to 5 ℃, slowly dripping 22.9g of methacrylic acid chloride under the condition of ice bath preparation, carrying hydrogen chloride gas generated in the reaction process into a sodium hydroxide solution sealer by nitrogen to react to generate sodium chloride and water, setting the dripping time to be 4 hours, continuing to react for 2 hours at constant temperature of 45 ℃ after finishing dripping, firstly decompressing at 50 ℃ to remove unreacted methacrylic acid chloride, then carrying out suction filtration to remove a solid catalyst in the liquid, washing with 5% potassium carbonate aqueous solution to be alkalescent, then washing with deionized water to be neutral, introducing the extracted oily liquid into an active carbon decoloring filter column to remove yellow substances, carrying out rotary evaporation at 55 ℃ to remove toluene and a small amount of water to obtain 114.0g of viscous colorless liquid containing 73.4g of methyl phosphonic acid bis (4' -hexafluorobisphenol A methacrylate), 40.6g of hexafluorobisphenol A dimethacrylate was used as a crosslinking flame retardant or for separation.
The yield of the flame retardant prepared in this example was 96.7%, the acid value was 0.023mgKOH/g, the molecular weight was 868.58, and the product was stored at low temperature.
Example 5
The flame retardant of this example is phenylphosphonic acid bis (4' -hexafluorobisphenol a methacrylate) ester, and the specific preparation method is as follows:
(1) a500 mL reactor was charged with 83.8g of hexafluorobisphenol A, 2.5g of anhydrous magnesium chloride, and 250g of toluene, nitrogen was introduced, and the tail gas was introduced into a 40% sodium hydroxide solution sealed vessel, the temperature was adjusted to 140 ℃, stirring was turned on, and 16.2g of phenylphosphonyl dichloride was slowly added dropwise over a period of 6 hours. After the dripping is finished, adjusting the temperature to 160 ℃, continuing to react for 2 hours, carrying hydrogen chloride gas generated in the reaction process into a sodium hydroxide solution sealer by nitrogen, reacting to generate sodium chloride and water, and fully reacting for 8 hours to obtain a hydroxyl-containing phenyl phosphonic acid bis (hexafluorobisphenol A) ester compound;
(2) after the temperature of the hydroxyl-containing phenylphosphonic acid bis (hexafluorobisphenol A) ester compound is reduced to 5 ℃, under the condition of ice bath preparation, 21.7g of methacryloyl chloride is slowly dripped, hydrogen chloride gas generated in the reaction process is carried into a sodium hydroxide solution sealer by nitrogen, and sodium chloride and water are generated by reaction, wherein the dripping time is set to 4 hours. After the dripping is finished, the reaction is continued for 2 hours at the constant temperature of 45 ℃, unreacted methacryloyl chloride is removed under reduced pressure at the temperature of 50 ℃, then the solid catalyst in the liquid is removed by suction filtration, and the liquid is washed to be alkaline by 8 percent potassium carbonate aqueous solution and then washed to be neutral by deionized water. The extracted oily liquid enters an activated carbon decoloration filter column to remove yellow substances, toluene and a small amount of water are removed by rotary evaporation at 55 ℃, and 112.5g of viscous colorless liquid, 74.1g of phenyl phosphonic acid di (4' -hexafluorobisphenol A methacrylate) and 38.4g of hexafluorobisphenol A dimethacrylate are obtained and can be directly used as a cross-linking flame retardant or used for separation.
The yield of the flame retardant prepared in this example was 95.9%, the acid value was 0.016mgKOH/g, the molecular weight was 930.65, and the product was stored at low temperature.
Example 6
The flame retardant of this example is bis (4' -hexafluorobisphenol a methacrylate) pentafluorophenyl phosphonate, the specific preparation method is as follows:
(1) adding 78.0g of bisphenol A, 3.0g of anhydrous zinc chloride and 250g of toluene into a 500mL reactor, introducing nitrogen, introducing tail gas into a 40% sodium hydroxide solution sealer, adjusting the temperature to 140 ℃, starting stirring, slowly dropwise adding 22.0g of pentafluorophosphonyl dichloride, setting the dropwise adding time to be 6 hours, adjusting the temperature to 160 ℃ after the dropwise adding is finished, continuing to react for 2 hours, carrying hydrogen chloride gas generated in the reaction process into the sodium hydroxide solution sealer by nitrogen, reacting to generate sodium chloride and water, and fully reacting for 8 hours to obtain a hydroxyl-containing bis (hexafluorobisphenol A) pentafluorophenylphosphonate compound;
(2) after the temperature of the hydroxyl-containing pentafluorophenyl phosphonic acid bis (hexafluorobisphenol A) ester compound is reduced to 5 ℃, under the condition of ice bath preparation, 20.2g of methacryloyl chloride is slowly dripped, hydrogen chloride gas generated in the reaction process is carried into a sodium hydroxide solution sealer by nitrogen to react to generate sodium chloride and water, the dripping time is set to 4 hours, after the dripping is finished, the reaction is continued for 2 hours at the constant temperature of 45 ℃, unreacted methacryloyl chloride is firstly removed under reduced pressure at 50 ℃, then, a solid catalyst in the liquid is removed by suction filtration, and the liquid is washed to be alkaline by 4% of potassium carbonate aqueous solution and then washed to be neutral by deionized water. The extracted oily liquid enters an activated carbon decoloration filter column to remove yellow substances, toluene and a small amount of water are removed by rotary evaporation at 55 ℃, and 115.4g of viscous colorless liquid containing 79.2g of pentafluorophenyl phosphonic acid di (4' -hexafluorobisphenol A methacrylate) and 36.2g of hexafluorobisphenol A dimethacrylate can be directly used as a crosslinking flame retardant or used for separation.
The yield of the flame retardant prepared in this example was 97.5%, the acid value was 0.019mgKOH/g, the molecular weight was 1050.60, and the product was stored at low temperature.
Test example 1
A PMMA sample is prepared by mixing the methyl phosphonic acid di (4' -bisphenol A methacrylate) ester flame retardant prepared in example 1 and methacrylate in different proportions under the initiation of 0.1% ammonium peroxysulfate initiator, and the limit oxygen index of the sample is measured by referring to GB/T2406-2008 ' Plastic burning performance test method-oxygen index method ', and the result is shown in Table 1.
TABLE 1
| Amount of flame retardant added (%) | 0 | 5 | 10 | 15 | 20 |
| LOI | 21 | 23 | 25 | 27 | 29 |
LOI 28 is the flame retardant limiting oxygen index, and it can be seen from Table 1 that 20% of di (4' -bisphenol A methacrylate) methylphosphonate can achieve the flame retardant effect, which is the effect of the combined action of crosslinking and flame retardant.
Test example 2
The bis (4' -bisphenol a methacrylate) phenylphosphonate flame retardant prepared in example 2 and methacrylate were initiated with 0.1% ammonium peroxysulfate initiator according to different ratios to prepare PMMA samples, and the limit oxygen index of the samples was measured with reference to GB/T2406-2008 "plastic combustion performance test method-oxygen index method", and the results are shown in table 2.
TABLE 2
| Amount of flame retardant added (%) | 0 | 5 | 10 | 15 | 20 |
| LOI | 21 | 24 | 26 | 30 | 33 |
LOI 28 is a flame-retardant limiting oxygen index, and it can be seen from Table 2 that 15% of phenyl phosphonic acid di (4' -bisphenol A methacrylate) ester can achieve a flame-retardant effect, which is an effect of combined action of crosslinking and flame-retardant, and the flame-retardant effect of phenyl phosphonate is obviously higher than that of methyl phosphonate.
Test example 3
A PMMA sample is prepared by mixing the bis (4' -hexafluorobisphenol A methacrylate) pentafluorophenylphosphonate flame retardant prepared in example 6 and methacrylate according to different proportions under the initiation of 0.1% ammonium peroxysulfate initiator, and the limit oxygen index of the sample is measured by referring to GB/T2406-2008 "Plastic burning Performance test method-oxygen index method", and the results are shown in Table 3.
TABLE 3
| Amount of flame retardant added (%) | 0 | 5 | 10 | 15 | 20 |
| LOI | 21 | 26 | 31 | 36 | 41 |
LOI 28 is a flame-retardant limit oxygen index, and it can be seen from Table 3 that 10% of bis (4' -hexafluorobisphenol A methacrylate) pentafluorophenyl phosphonate can achieve a flame-retardant effect, which is an effect of a combined action of crosslinking and flame-retardant, and at the same time, fluorine-containing substances also achieve a certain flame-retardant effect.
The inventors also conducted the above tests on the flame retardants prepared in other examples, and the results were substantially consistent and, due to the limited space, are not listed.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A preparation method of a dual-reaction type phosphonate ester cross-linking flame retardant is characterized by comprising the following steps:
(1) reacting organic phosphonic dichloride and an excessive dihydroxy compound under the conditions of a solvent and a Lewis acid catalyst to obtain a hydroxyl-containing phosphonate compound;
(2) and cooling the hydroxyl-containing phosphonate compound to 0-7 ℃, slowly dropwise adding acryloyl halide, reacting at the constant temperature of 30-50 ℃ for 1.5-2.5 h, and performing suction filtration, alkali washing, water washing, separation, color removal and distillation to obtain the double-reaction type phosphonate cross-linking flame retardant.
2. The method for preparing a dual-reaction type phosphonate ester cross-linking flame retardant of claim 1, wherein the organic phosphonic dichloride in the step (1) is one of methyl phosphonic dichloride, phenyl phosphonic dichloride and pentafluorophenyl phosphonic dichloride, and the dihydroxy compound is bisphenol A or hexafluorobisphenol A.
3. The method for preparing a dual-reaction type phosphonate cross-linking flame retardant of claim 1, wherein the solvent in step (1) is one of benzene, toluene and xylene, and the Lewis acid catalyst is one of anhydrous aluminum trichloride, anhydrous magnesium bromide, anhydrous magnesium chloride and anhydrous zinc chloride.
4. The preparation method of the dual-reaction type phosphonate ester cross-linking flame retardant of claim 1, wherein the reaction temperature in the step (1) is 140-160 ℃ and the reaction time is 7-9 hours.
5. The preparation method of the dual-reaction type phosphonate ester cross-linking flame retardant of claim 1, wherein the molar ratio of the organic phosphonic dichloride and the dihydroxy compound in the step (1) is 1: 2.5-5.0, the mass ratio of the total mass of the organic phosphonic dichloride and the dihydroxy compound to the solvent is 100: 250-500, and the mass ratio of the total mass of the organic phosphonic dichloride and the dihydroxy compound to the Lewis acid catalyst is 100: 1.0-5.0.
6. The preparation method of the dual-reaction type phosphonate ester cross-linking flame retardant of claim 1, wherein the tail gas generated in the reaction process is collected in the steps (1) and (2) and reacts with a sodium hydroxide solution to generate sodium halide and water.
7. The method for preparing a dual-reaction type phosphonate ester cross-linking flame retardant of claim 1, wherein the acryloyl halide in the step (2) is one of acryloyl chloride, acryloyl bromide, methacryloyl chloride or methacryloyl bromide.
8. The preparation method of the dual-reaction type phosphonate ester cross-linking flame retardant of claim 1, wherein the molar ratio of the hydroxyl-containing phosphonate compound to the acryloyl halide in the step (2) is 1: 2.5-5.0.
9. The preparation method of the dual-reaction phosphonate cross-linking flame retardant of claim 1, wherein the alkali washing in the step (2) is performed by washing the column with 2-8% potassium carbonate aqueous solution, and the column is washed with activated carbon for color removal.
10. A dual-reactive phosphonate cross-linking flame retardant prepared by the method of any one of claims 1 to 9.
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