CN114539313B - Double-reaction type phosphonate crosslinking flame retardant and preparation method thereof - Google Patents
Double-reaction type phosphonate crosslinking flame retardant and preparation method thereof Download PDFInfo
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- CN114539313B CN114539313B CN202210168726.0A CN202210168726A CN114539313B CN 114539313 B CN114539313 B CN 114539313B CN 202210168726 A CN202210168726 A CN 202210168726A CN 114539313 B CN114539313 B CN 114539313B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 84
- 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 68
- 238000004132 cross linking Methods 0.000 title claims abstract description 23
- 238000006757 chemical reactions by type Methods 0.000 title claims abstract description 22
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- -1 phosphonate compound Chemical class 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910001868 water Inorganic materials 0.000 claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 125000005499 phosphonyl group Chemical group 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
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000004042 decolorization Methods 0.000 claims abstract description 5
- 239000003513 alkali Substances 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 22
- 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 18
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 238000004519 manufacturing process Methods 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
- 239000000463 material Substances 0.000 abstract description 25
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract description 17
- 239000004926 polymethyl methacrylate Substances 0.000 abstract description 17
- 239000003431 cross linking reagent Substances 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 239000007788 liquid Substances 0.000 description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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 18
- 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
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical group OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 7
- 239000011949 solid catalyst Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 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
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 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 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 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 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
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 239000012935 ammoniumperoxodisulfate Substances 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
- 239000003999 initiator Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 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 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010998 test method Methods 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 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
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 229920001523 phosphate polymer Polymers 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000979 retarding effect Effects 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
- 238000010025 steaming Methods 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 System
- 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, i.e. RP(=X)(XH)2 (X = S, 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)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to a double-reaction type phosphonate crosslinking flame retardant and a preparation method thereof, comprising the following steps: reacting organic phosphonyl dichloride with excessive dihydroxy compound under the conditions of a solvent and a Lewis acid catalyst to obtain a phosphonate compound containing hydroxyl; and (3) cooling the hydroxyl-containing phosphonate compound to 0-7 ℃, slowly dropwise adding acrylic halide, and carrying out suction filtration, alkali washing, water washing, separation, color removal and distillation to obtain the double-reaction type phosphonate crosslinking flame retardant. The double-reaction type phosphonate crosslinking flame retardant disclosed by the invention is added into PMMA as a reaction type flame retardant, not only plays a flame retardant role, but also can be used as a crosslinking agent of a reaction monomer, the performance of PMMA material is not affected, the prepared PMMA material is good in transparency, and the flame retardant prepared by the method disclosed by the invention is high in yield, simple in process, low in cost and suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a double-reaction type phosphonate crosslinking flame retardant and a preparation method thereof.
Background
To avoid spontaneous combustion or heated combustion of the organic material, a certain amount of flame retardant is typically added to the organic material. Flame retardants are classified into additive type and reactive type: the adding type is small molecular substances, the adding amount is usually 10-40%, and the using amount is relatively large, so that the mechanical property or optical property of the material can be influenced, the material is combined with the main material by adsorption, and the material is unevenly distributed in the main material, so that the mechanical property of the material can be influenced; the reaction type material 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 uniform in distribution, and does not influence the mechanical properties of the material. The reactive flame retardant has the advantages that: can be used as a polymer molecular monomer and can resist flame. Reactive flame retardants are particularly important in the future for high new materials, relative to additive flame retardants.
Currently, reactive flame retardants are limited to only partially brominated flame retardants, such as tribromophenyl acrylate or tribromophenyl methacrylate, and other types are rarely reactive. Although brominated flame retardants are a class of classical flame retardants and are internationally accepted, yellow bromine released by combustion is extremely toxic and therefore is slowly sloping towards phosphorus flame retardants in use. The phosphorus flame retardant has low toxicity and the use amount is continuously increasing. However, most phosphorus flame retardants are small molecules or small molecular weight polymers, and reactive phosphorus flame retardants are rarely seen. Especially in PMMA materials, the flame retardant tends to influence the transparency of the material, most of the flame retardant is not suitable for the PMMA material, so that the PMMA material is little added with the flame retardant, and the application of the PMMA material added with the flame retardant is greatly expanded. Whereas the PMMA material added with flame retardant is mostly added with a small molecular weight phosphate polymer. In practical production, it is found that when preparing PMMA materials with high strength and high transparency, a proper double-reaction type phosphonate crosslinking flame retardant is urgently needed, and the flame retardant is a crosslinking agent of a reaction monomer and plays a role in improving the material property as a whole.
The present invention has been made in view of the above-mentioned circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the double-reaction type phosphonate crosslinked flame retardant and the preparation method thereof, and the flame retardant prepared by the method has high yield, can be used as a flame retardant of PMMA materials, can be used as a crosslinking agent at the same time, and can improve the overall properties of the PMMA materials.
The first object of the invention is to provide a preparation method of a double-reaction type phosphonate crosslinking flame retardant, which comprises the following steps:
(1) Reacting organic phosphonyl dichloride with excessive dihydroxy compound under the conditions of a solvent and a Lewis acid catalyst to obtain a phosphonate compound containing hydroxyl;
(2) Cooling the hydroxyl-containing phosphonate compound to 0-7 ℃, slowly dropwise adding acryloyl halide, reacting for 1.5-2.5 hours at a constant temperature of 30-50 ℃, and obtaining the double-reaction type phosphonate crosslinking flame retardant through suction filtration, alkali washing, water washing, separation, color removal and distillation.
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 to 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, the tail gas generated in the reaction process is collected in the steps (1) and (2) to react with sodium hydroxide solution to generate sodium halide and water.
Further, the acrylic acid halide in the step (2) is one of acrylic acid chloride, acrylic acid bromide, methacrylic acid chloride or methacrylic acid bromide.
Further, the molar ratio of the phosphonate compound containing hydroxyl group to the acrylic acid halide in the step (2) is 1:2.5-5.0.
Further, in the step (2), the alkaline washing is performed by using a potassium carbonate aqueous solution with the concentration of 2-8%, and the column is leached by using activated carbon for color removal.
The second object of the invention is to provide a double-reaction type phosphonate crosslinking flame retardant prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
The double-reaction type phosphonate crosslinking flame retardant disclosed by the invention is added into PMMA as a reaction type flame retardant, not only plays a flame retardant role, but also can be used as a crosslinking agent of a reaction monomer, the performance of PMMA material is not affected, and the prepared PMMA material is good in transparency, so that the double-reaction type phosphonate crosslinking flame retardant is a brand-new type of phosphine flame retardant, and the flame retardant prepared by the method disclosed by the invention is high in yield, simple in process, low in cost and suitable for mass 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 will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
Example 1
The flame retardant of this example is bis (4' -bisphenol a methacrylate) methylphosphonate, and the specific preparation method is as follows:
(1) 83.8g of bisphenol A,4.0g of anhydrous aluminum trichloride and 250g of toluene are added into a 500mL reactor, nitrogen is introduced, tail gas is introduced into a 40% sodium hydroxide solution sealer, the temperature is adjusted to 140 ℃, 16.2g of methylphosphonic dichloride is slowly added dropwise under stirring, the dropwise adding time is set to 6 hours, and after the dropwise adding, the temperature is adjusted to 160 ℃ and the reaction is continued for 2 hours. The 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 hydroxy-containing methyl phosphonic acid bisphenol A ester compound is obtained after full reaction for 8 hours;
(2) After the temperature of the hydroxy-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 firstly removed under reduced pressure at 50 ℃, then solid catalyst in liquid is removed by suction filtration, 4% potassium carbonate aqueous solution is used for washing to be slightly alkaline, deionized water is used for washing to be neutral, extracted oily liquid enters an activated carbon decoloration filter column, yellow substances are removed, toluene and a small amount of water are removed by rotary evaporation at 55 ℃ to obtain 121.1g of viscous colorless liquid, 77.0g of bis (4' -bisphenol A methacrylate) ester containing methylphosphonic acid and 44.1g of bisphenol A dimethacrylate are contained, and the liquid can be directly used as a crosslinking flame retardant or used for separation.
The flame retardant prepared in this example had a yield of 96.5%, an acid value of 0.020mgKOH/g, a molecular weight of 652.69, and a low-temperature storage of the product.
Example 2
The flame retardant in the embodiment is phenyl phosphonic acid di (4' -bisphenol A methacrylate) ester, and the specific preparation method is as follows:
(1) 77.8g of bisphenol A, 4.5g of anhydrous magnesium chloride and 275g of benzene are added into a 500mL reactor, nitrogen is introduced, the temperature of the tail gas is adjusted to 140 ℃ in a 40% sodium hydroxide solution sealer, stirring is started, 22.2g of phenylphosphonic dichloride is slowly added dropwise, and the dropwise adding time is set to 6 hours. After the dripping is finished, the temperature is adjusted to 160 ℃, the reaction is continued for 2 hours, 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 the reaction, and the hydroxy-containing phenylphosphonic acid bisphenol A ester compound is obtained after 8 hours of full reaction;
(2) After the temperature of the hydroxyl-containing phenylphosphonic acid bisphenol A ester compound is reduced to 5 ℃, 30.2g of methacryloyl chloride is slowly dripped under the condition of ice bath preparation, 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, the reaction is continued for 2 hours at the constant temperature of 45 ℃, unreacted methacryloyl chloride is removed under reduced pressure at 50 ℃, then solid catalyst in liquid is removed by suction filtration, the liquid is washed to be slightly alkaline by 5% potassium carbonate aqueous solution, and then the liquid is washed to be neutral by deionized water. The extracted oily liquid enters an activated carbon decoloring and filtering 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 bis (4' -bisphenol A methacrylate) ester containing phenylphosphonic acid, and 40.6g of bisphenol A dimethacrylate, which can be directly used as a crosslinking flame retardant or used for separation.
The flame retardant was produced in this example in a yield of 95.8%, an acid value of 0.018mgKOH/g, a molecular weight of 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 prepared by the following method:
(1) 70.6g of bisphenol A, 3.5g of anhydrous zinc chloride, 325g of xylene and nitrogen are added into a 500mL reactor, the temperature of the mixture is adjusted to 140 ℃ in a 40% sodium hydroxide solution sealer into which tail gas is introduced, stirring is started, 29.4g of pentafluorophenyl phosphonodichloride is slowly added dropwise, and the dropwise adding time is set to 6 hours. After the dripping is finished, the temperature is adjusted to 160 ℃, the reaction is continued for 3 hours, 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 the reaction, and after 9 hours, the reaction is fully carried out, and the hydroxyl-containing pentafluorophenyl phosphonic acid bisphenol A ester compound is obtained;
(2) After the temperature of the hydroxyl-containing pentafluorophenyl phosphonic acid bisphenol A ester compound is reduced to 7 ℃, 26.9g of methacryloyl chloride is slowly dripped under the condition of ice bath preparation, 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, the dripping time is set to be 4 hours, after dripping is finished, the reaction is continued for 1.5 hours at the constant temperature of 50 ℃, and 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 5% potassium carbonate aqueous solution and then is washed to be neutral by deionized water. The extracted oily liquid enters an activated carbon decoloring and filtering column to remove yellow substances, xylene and a small amount of water are removed by rotary evaporation at 60 ℃ to obtain 123.1g of viscous colorless liquid, 86.0g of bis (4' -bisphenol A methacrylate) pentafluorophenyl phosphonate and 37.1g of bisphenol A dimethacrylate are contained, and the viscous colorless liquid can be directly used as a crosslinking flame retardant or used for separation.
The flame retardant prepared in this example had a yield of 95.1%, an acid value of 0.021mgKOH/g, a molecular weight of 834.72, and a low-temperature storage of the product.
Example 4
The flame retardant of this example is bis (4' -hexafluorobisphenol A methacrylate) methylphosphonate, and the specific preparation method is as follows:
(1) 88.4g of hexafluorobisphenol A, 4.0g of anhydrous magnesium bromide and 250g of toluene are added into a 500mL reactor, nitrogen is introduced, the temperature is adjusted to 140 ℃ in a 40% sodium hydroxide solution sealer into which tail gas is introduced, stirring is started, 11.6g of methylphosphonic dichloride is slowly added dropwise, and the dropwise adding time is set to 6 hours. After the dripping is finished, the temperature is adjusted to 160 ℃, the reaction is continued for 2 hours, 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 the reaction, and the hydroxy-containing methyl phosphonic acid bis (hexafluorobisphenol A) ester compound is obtained after 8 hours of full reaction;
(2) Cooling the hydroxyl-containing methyl phosphonic acid bis (hexafluorobisphenol A) ester compound to 5 ℃, slowly dropwise adding 22.9g of methyl acryloyl 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, reacting to generate sodium chloride and water, setting the dropwise adding time to be 4 hours, continuously reacting for 2 hours at the constant temperature of 45 ℃, firstly removing unreacted methyl acryloyl chloride under reduced pressure at 50 ℃, then removing a solid catalyst in liquid by suction filtration, washing to be alkaline by using a 5% potassium carbonate aqueous solution, washing to be neutral by using deionized water, introducing the extracted oily liquid into an active carbon decoloration filter column, removing yellow substances, rotationally steaming at 55 ℃ to remove toluene and a small amount of water, obtaining 114.0g of viscous colorless liquid, namely 73.4g of methyl phosphonic acid bis (4' -hexafluorobisphenol A methacrylate), and 40.6g of hexafluorobisphenol A dimethacrylate, wherein the solid catalyst can be directly used as a crosslinking flame retardant or used for separation.
The flame retardant prepared in this example was 96.7% in yield, 0.023mgKOH/g in acid value, 868.58 in molecular weight, and the product was stored at low temperature.
Example 5
The flame retardant of this example is phenyl phosphonic acid bis (4' -hexafluorobisphenol A methacrylate) ester, and the specific preparation method is as follows:
(1) 83.8g of hexafluorobisphenol A, 2.5g of anhydrous magnesium chloride and 250g of toluene are added into a 500mL reactor, nitrogen is introduced, the temperature is adjusted to 140 ℃ in a 40% sodium hydroxide solution sealer into which tail gas is introduced, stirring is started, 16.2g of phenylphosphonic dichloride is slowly added dropwise, and the dropwise adding time is set to 6 hours. After the dripping is finished, the temperature is adjusted to 160 ℃, the reaction is continued for 2 hours, 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 the reaction, and the hydroxyl-containing phenyl phosphonic acid bis (hexafluorobisphenol A) ester compound is obtained after 8 hours of full reaction;
(2) After the temperature of the hydroxyl-containing phenyl phosphonic acid di (hexafluorobisphenol A) ester compound is reduced to 5 ℃, 21.7g of methacryloyl chloride is slowly added dropwise under the condition of ice bath preparation, 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 dropwise adding time is set to be 4 hours. After the dripping, the reaction is continued for 2 hours at the constant temperature of 45 ℃, unreacted methacryloyl chloride is removed under reduced pressure at 50 ℃, then solid catalyst in liquid is removed by suction filtration, the liquid is washed to be slightly alkaline by 8% potassium carbonate aqueous solution, and then the liquid is washed to be neutral by deionized water. The extracted oily liquid enters an activated carbon decoloring and filtering column to remove yellow substances, toluene and a small amount of water are removed by rotary evaporation at 55 ℃ to obtain 112.5g of viscous colorless liquid, 74.1g of phenyl phosphonic acid di (4' -hexafluorobisphenol A methacrylate) ester and 38.4g of hexafluorobisphenol A dimethacrylate are contained, and the viscous colorless liquid can be directly used as a crosslinking flame retardant or used for separation.
The flame retardant prepared in this example had a yield of 95.9%, an acid value of 0.016mgKOH/g, a molecular weight of 930.65, and a low-temperature storage of the product.
Example 6
The flame retardant of this example is bis (4' -hexafluorobisphenol A methacrylate) pentafluorophenyl phosphonate, which is prepared by the following method:
(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 ℃, opening stirring, slowly dropwise adding 22.0g of pentafluorophosphonic dichloride, setting the dropwise adding time to be 6 hours, adjusting the temperature to 160 ℃ after dropwise adding, 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) pentafluorophenyl phosphonate compound;
(2) Cooling the hydroxyl-containing pentafluorophenyl phosphonic acid bis (hexafluorobisphenol A) ester compound to 5 ℃, slowly dropwise adding 20.2g 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, reacting to generate sodium chloride and water, setting the dropwise adding time to be 4 hours, continuing to react for 2 hours at the constant temperature of 45 ℃, firstly decompressing at 50 ℃, removing unreacted methacryloyl chloride, removing a solid catalyst in liquid by suction filtration, washing to be slightly alkaline by using a 4% potassium carbonate aqueous solution, and washing to be neutral by deionized water. The extracted oily liquid enters an activated carbon decoloring and filtering column to remove yellow substances, toluene and a small amount of water are removed by rotary evaporation at 55 ℃ to obtain 115.4g of viscous colorless liquid, 79.2g of bis (4' -hexafluorobisphenol A methacrylate) ester containing pentafluorophenyl phosphonic acid and 36.2g of hexafluorobisphenol A dimethacrylate are contained, and the viscous colorless liquid can be directly used as a crosslinking flame retardant or used for separation.
The flame retardant prepared in this example was produced in a yield of 97.5%, an acid value of 0.019mgKOH/g, a molecular weight of 1050.60, and the product was stored at a low temperature.
Test example 1
The methyl phosphonic acid di (4' -bisphenol A methacrylate) flame retardant prepared in example 1 is mixed with methacrylate according to different proportions and initiated by 0.1% ammonium peroxodisulfate initiator to prepare PMMA sample, and the limiting oxygen index of the sample is measured by referring to GB/T2406-2008 "test method for Plastic Combustion Performance-oxygen index method", and the results are shown in Table 1.
TABLE 1
| Flame retardant addition (%) | 0 | 5 | 10 | 15 | 20 |
| LOI | 21 | 23 | 25 | 27 | 29 |
LOI 28 is the fire-retardant limiting oxygen index, and it can be seen from Table 1 that a fire-retardant effect can be achieved by adding 20% of bis (4' -bisphenol A methacrylate) methylphosphonate, which is the effect of both crosslinking and fire retarding.
Test example 2
The phenyl phosphonic acid di (4' -bisphenol A methacrylate) flame retardant prepared in example 2 is prepared into PMMA samples according to different proportions with methacrylate under the initiation of 0.1% ammonium peroxodisulfate initiator, and the limiting oxygen index of the samples is measured by referring to GB/T2406-2008 "test method for Plastic Combustion Performance-oxygen index method", and the results are shown in Table 2.
TABLE 2
| Flame retardant addition (%) | 0 | 5 | 10 | 15 | 20 |
| LOI | 21 | 24 | 26 | 30 | 33 |
LOI 28 is the fire-retardant limiting oxygen index, and from Table 2, it can be seen that the flame-retardant effect can be achieved by adding 15% of the di (4' -bisphenol A methacrylate) phenylphosphonate, which is the effect of the combined action of crosslinking and flame retardance, and the flame-retardant effect of the phenylphosphonate is obviously higher than that of the methylphosphonate.
Test example 3
PMMA samples prepared by mixing the pentafluorophenyl phosphonic acid bis (4' -hexafluorobisphenol A methacrylate) flame retardant prepared in example 6 with methacrylate according to different proportions under the initiation of 0.1% ammonium peroxodisulfate initiator are prepared, and the limiting oxygen index of the samples is measured by referring to GB/T2406-2008 "method for testing Plastic Combustion Performance-oxygen index method", and the results are shown in Table 3.
TABLE 3 Table 3
| Flame retardant addition (%) | 0 | 5 | 10 | 15 | 20 |
| LOI | 21 | 26 | 31 | 36 | 41 |
LOI 28 is the fire-retardant limiting oxygen index, and it can be seen from Table 3 that the flame-retardant effect can be achieved by adding 10% of bis (4' -hexafluorobisphenol A methacrylate) pentafluorophenyl phosphonate, which is the effect of the combined action of crosslinking and flame retardance, and the fluorine-containing compound also has a certain flame-retardant effect.
The inventors have also conducted the above-described tests on the flame retardants prepared in the other examples, and the results are substantially identical and are not listed here again because of limited space.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. The preparation method of the double-reaction type phosphonate crosslinked flame retardant is characterized by comprising the following steps of:
(1) Reacting organic phosphonyl dichloride with excessive dihydroxy compound under the conditions of a solvent and a Lewis acid catalyst to obtain a phosphonate compound containing hydroxyl;
(2) Cooling the hydroxyl-containing phosphonate compound to 0-7 ℃, slowly dropwise adding acryloyl halide, reacting at a constant temperature of 30-50 ℃ for 1.5-2.5 hours, and obtaining the double-reaction type phosphonate crosslinked flame retardant through suction filtration, alkali washing, water washing, separation, color removal and distillation;
In the step (1), the organic phosphonyl dichloride is one of methyl phosphonyl dichloride, phenyl phosphonyl dichloride and pentafluorophenyl phosphonyl dichloride, and the dihydroxy compound is bisphenol A or hexafluorobisphenol A;
the solvent is one of benzene, toluene and xylene;
The Lewis acid catalyst is one of anhydrous aluminum trichloride, anhydrous magnesium bromide, anhydrous magnesium chloride and anhydrous zinc chloride.
2. The method for preparing a double-reaction type phosphonate crosslinking flame retardant according to claim 1, wherein the reaction temperature in the step (1) is 140-160 ℃ and the reaction time is 7-9 hours.
3. The preparation method of the double-reaction type phosphonate crosslinking flame retardant according to claim 1, wherein in the step (1), the molar ratio of the organic phosphonyl dichloride to 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.
4. The method for preparing a double-reaction type phosphonate crosslinked flame retardant according to claim 1, wherein the tail gas generated in the reaction process is collected in the steps (1) and (2) to react with sodium hydroxide solution to generate sodium halide and water.
5. The method for preparing a double-reactive phosphonate crosslinked flame retardant according to claim 1, wherein the acrylic acid halide in the step (2) is one of acrylic acid chloride, acrylic acid bromide, methacrylic acid chloride or methacrylic acid bromide.
6. The method for producing a double-reactive phosphonate crosslinked flame retardant according to claim 1, wherein the molar ratio of the hydroxyl-containing phosphonate compound to the acryl halide in the step (2) is 1:2.5-5.0.
7. The method for preparing a double-reaction type phosphonate crosslinked flame retardant according to claim 1, wherein in the step (2), alkali washing is carried out by using a potassium carbonate aqueous solution with the concentration of 2-8%, and the column is leached by using activated carbon for color removal.
8. A dual-reactive phosphonate crosslinked flame retardant prepared by the method of any one of claims 1-7.
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| EP2655383B1 (en) * | 2010-12-22 | 2017-03-01 | FRX Polymers, Inc. | Hyperbranched oligomeric phosphonates and compositions including the same |
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