CN114573634B - Pentafluorophenyl phosphonic acid di (pentafluorophenyl) ester flame retardant and preparation method thereof - Google Patents
Pentafluorophenyl phosphonic acid di (pentafluorophenyl) ester flame retardant and preparation method thereof Download PDFInfo
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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 39
- 239000003063 flame retardant Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- IQWKYBVDHFFDSW-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-[(2,3,4,5,6-pentafluorophenoxy)-(2,3,4,5,6-pentafluorophenyl)phosphoryl]oxybenzene Chemical compound O=P(C(C(F)=C(C(F)=C1F)F)=C1F)(OC(C(F)=C(C(F)=C1F)F)=C1F)OC(C(F)=C(C(F)=C1F)F)=C1F IQWKYBVDHFFDSW-UHFFFAOYSA-N 0.000 title claims abstract description 13
- -1 pentafluorophenyl phosphine dichloride Chemical compound 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 16
- AMQDBUIQKQUCKY-UHFFFAOYSA-M magnesium;1,2,3,4,5-pentafluorobenzene-6-ide;bromide Chemical compound [Mg+2].[Br-].FC1=[C-]C(F)=C(F)C(F)=C1F AMQDBUIQKQUCKY-UHFFFAOYSA-M 0.000 claims abstract description 13
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 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 abstract description 12
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- LQVWMWVNQKLCSQ-UHFFFAOYSA-N (2,3,4,5-tetrafluoro-6-phenylphenyl) hypofluorite Chemical compound FOC1=C(F)C(F)=C(F)C(F)=C1C1=CC=CC=C1 LQVWMWVNQKLCSQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000003747 Grignard reaction Methods 0.000 claims abstract description 5
- 238000004042 decolorization Methods 0.000 claims abstract description 5
- QJZOVDPHILFRTD-UHFFFAOYSA-N dichloro-(2,3,4,5,6-pentafluorophenyl)phosphane Chemical compound FC1=C(F)C(F)=C(P(Cl)Cl)C(F)=C1F QJZOVDPHILFRTD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 238000005886 esterification reaction Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 9
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 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
- XEKTVXADUPBFOA-UHFFFAOYSA-N 1-bromo-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(Br)C(F)=C1F XEKTVXADUPBFOA-UHFFFAOYSA-N 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- BBRZBPOCCPEBBU-UHFFFAOYSA-L magnesium;dichloride;hydrochloride Chemical compound [Mg+2].Cl.[Cl-].[Cl-] BBRZBPOCCPEBBU-UHFFFAOYSA-L 0.000 claims description 2
- CRUISIDZTHMGJT-UHFFFAOYSA-L zinc;dichloride;hydrochloride Chemical compound Cl.[Cl-].[Cl-].[Zn+2] CRUISIDZTHMGJT-UHFFFAOYSA-L 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 15
- 239000004926 polymethyl methacrylate Substances 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000002940 repellent Effects 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 125000001207 fluorophenyl group Chemical group 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- FAGFGFAOZZJLLR-UHFFFAOYSA-N 1-(2-bromophenyl)-2,3,4,5,6-pentafluorobenzene Chemical compound BrC1=C(C=CC=C1)C1=C(C(=C(C(=C1F)F)F)F)F FAGFGFAOZZJLLR-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical group [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3282—Esters with hydroxyaryl compounds
-
- 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3229—Esters of aromatic acids (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5337—Esters of phosphonic acids containing also halogens
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- 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)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a pentafluorophenyl phosphonic acid di (pentafluorophenyl) ester flame retardant and a preparation method thereof, wherein the method comprises the following steps: carrying out Grignard reaction on pentafluorobromide and magnesium powder in tetrahydrofuran to generate pentafluorophenyl magnesium bromide, and adding phosphorus trichloride into the pentafluorophenyl magnesium bromide to react to generate pentafluorophenyl phosphine dichloride; the pentafluorophenyl phosphorus dichloride is subjected to high-temperature oxidation reaction in the presence of a phenylphosphonic acid solvent to obtain pentafluorophenyl phosphono dichloride; the pentafluorophenyl phosphonic dichloride and the pentafluorophenyl phenol are subjected to esterification reaction in a catalyst and a solvent, and the pentafluorophenyl phosphonic acid di (pentafluorophenyl) ester is obtained through alkali washing, water washing, separation, color removal and distillation. The novel flame retardant prepared by the method has the advantages of excellent flame retardant effect, excellent heat resistance, anti-fog property, water repellency and the like, and has the characteristics that: the preparation method is simple, high in yield, low in production 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 bis (pentafluorophenyl) pentafluorophenyl phosphonate flame retardant and a preparation method thereof.
Background
PMMA materials are widely used in aircraft glass, motor car glass, automobile glass, lenses, periscope, glasses and the like because of their transparency and impact resistance far stronger than inorganic glass. Because PMMA material belongs to low refractive index material, the refractive index of common brominated flame retardant and phosphorus flame retardant is higher, if common brominated flame retardant or phosphorus flame retardant is added into PMMA material, the light transmittance of PMMA material is inevitably reduced, and the turbidity of material is increased; if the flame retardant is not added, the PMMA material is a combustible material, so that the application of the PMMA material is necessarily limited. Aircraft glass, motor car glass and automobile glass belong to high-quality products, and the quality requirements of light transmittance, organoleptic properties, flame resistance and the like are very high. Therefore, the preparation of the flame retardant which is suitable for PMMA materials becomes an urgent problem to be solved in the industry. Dimethyl methylphosphonate (DMMP) flame retardant can meet the common flame retardance, but cannot meet the performances of high temperature resistance, fog resistance, water repellency, and the like.
Patent CN104725668a discloses a novel phosphorus-silicon flame retardant containing a fluorophenyl group and a phosphate structure, which contains a pentafluorophenyl group, a phosphate and a phosphorus-oxygen structure. The flame retardant has high temperature resistance, but has no outstanding anti-fog, water repellent and other performances. Not only aircraft glass, motor car glass, car glass need fine antifogging, water repellent etc. performance, but also lens, periscope, glasses etc. also need fine antifogging, water repellent etc. performance.
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 pentafluorophenyl phosphonic acid di (pentafluorophenyl) ester flame retardant and the preparation method thereof, and the method provided by the invention prepares a brand new flame retardant which not only has excellent flame retardant effect, but also has excellent performances such as heat resistance, anti-fog property, water repellency and the like.
The first object of the invention is to provide a preparation method of a bis (pentafluorophenyl) pentafluorophenyl phosphonate flame retardant, which is characterized in that the method comprises the following steps:
(1) Preparation of pentafluorophenyl phosphine dichloride: carrying out Grignard reaction on pentafluorobromide and magnesium powder in tetrahydrofuran to generate pentafluorophenyl magnesium bromide, and adding phosphorus trichloride into the pentafluorophenyl magnesium bromide to react to generate pentafluorophenyl phosphine dichloride;
(2) Preparation of pentafluorophenyl phosphonic dichloride: the pentafluorophenyl phosphorus dichloride is subjected to high-temperature oxidation reaction under phenylphosphonic acid to obtain pentafluorophenyl phosphono dichloride;
(3) Preparation of bis (pentafluorophenyl) pentafluorophenyl phosphonate: the pentafluorophenyl phosphonic dichloride and the pentafluorophenyl phenol are subjected to esterification reaction under the condition of a catalyst, and the pentafluorophenyl phosphonic acid di (pentafluorophenyl) ester is obtained through alkali washing, water washing, separation, color removal and distillation.
Further, the Grignard reaction temperature in the step (1) is 50-65 ℃ and the reaction time is 7-8 hours.
Further, in the step (1), the mass ratio of the pentafluorobromide benzene to the tetrahydrofuran is 100:350-510, wherein the molar ratio of the pentafluorobromobenzene to the magnesium powder is 1:1-1.05, and the molar ratio of the pentafluorophenyl magnesium bromide to the phosphorus trichloride is 1:1.2-1.5.
Further, in the step (1), the reaction temperature of the pentafluorophenyl magnesium bromide and the phosphorus trichloride is 75-81 ℃, and the reaction time is 7-9 hours.
Further, in the step (2), the high-temperature oxidation reaction temperature is 200-250 ℃, the reaction time is 5-7 hours, and the mass ratio of the pentafluorophenyl phosphorus dichloride to the phenylphosphonic acid is 100:200-550.
Further, in the step (3), the molar ratio of the pentafluorophenyl phosphonic dichloride to the pentafluorophenyl phenol is 1:2-2.6, and the mass ratio of the total mass of the pentafluorophenyl phosphonic dichloride and the pentafluorophenyl phenol to the catalyst is 100:2-5.
Further, the solvent in the step (3) is one of benzene, toluene and xylene, and the mass ratio of pentafluorophenyl phosphonic dichloride to the solvent is 100:250-440.
Further, in the step (3), the catalyst is one of anhydrous magnesium trichloride, anhydrous aluminum trichloride, anhydrous zinc trichloride and anhydrous magnesium bromide.
Further, in the step (3), the alkaline washing adopts a potassium carbonate aqueous solution with the mass fraction of 2-8%, and the color removal adopts an activated carbon leaching column.
The second object of the invention is to provide a bis (pentafluorophenyl) pentafluorophenyl phosphonate flame retardant prepared by the process.
Compared with the prior art, the invention has the beneficial effects that:
The novel pentafluorophenyl phosphonic acid di (pentafluorophenyl) ester flame retardant prepared by the method has the advantages of excellent flame retardant effect, low toxicity, excellent heat resistance, anti-fog property, water repellency and the like, and is used for producing PMMA materials, and the flame retardant has the characteristics of: the preparation method is simple, high in yield, low in production 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 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 preparation method of the pentafluorophenyl phosphonic acid di (pentafluorophenyl) ester flame retardant in the embodiment specifically comprises the following steps:
(1) Preparation of pentafluorophenyl phosphine dichloride:
Adding 4.9g of magnesium powder and 250g of tetrahydrofuran into a 500mL reactor, introducing nitrogen, stirring, heating to 50 ℃, slowly dripping 49.4g of pentafluorobromide benzene, setting the reaction time to 7.5 hours, obtaining pentafluorophenyl magnesium bromide after the reaction is finished, slowly adding 50g of phosphorus trichloride, gradually heating to 78 ℃, carrying out reflux reaction for 8 hours, removing salt by suction filtration, and then removing tetrahydrofuran and redundant phosphorus trichloride by distillation to obtain pentafluorophenyl phosphine dichloride with molecular weight 233.49 and yield of 81.5%;
(2) Preparation of pentafluorophenyl phosphonic dichloride:
Adding 46.7g of pentafluorophenyl phosphine dichloride and 250g of anhydrous phenylphosphonic acid into a 500mL reactor, introducing nitrogen, stirring, heating to 250 ℃, slowly introducing pure oxygen, observing reflux condition, ending the reaction after 6 hours, and evaporating the phenylphosphonic acid under reduced pressure to obtain pentafluorophenyl phosphonodichloride with molecular weight 284.93 and yield of 96.7%;
(3) Preparation of bis (pentafluorophenyl) pentafluorophenyl phosphonate:
In a 500mL reactor, 57.0g of pentafluorophenyl phosphonyl dichloride, 87g of pentafluorophenol, 6g of anhydrous aluminum chloride and 250g of toluene are added, nitrogen is introduced and stirred, the temperature is increased to 145 ℃, the reflux reaction is carried out for 8 hours, hydrogen chloride gas generated in the process is carried into a sodium hydroxide solution sealer by the nitrogen through a tail pipe, after the reaction is finished, solid catalyst in liquid is removed by suction filtration, solvent toluene and superfluous pentafluorophenol are distilled off under reduced pressure, thus obtaining a crude product of bis (pentafluorophenyl) pentafluorophenyl phosphonate, 250g of toluene is added to dissolve bis (pentafluorophenyl) pentafluorophenyl phosphonate, 4% potassium carbonate aqueous solution is used for washing to be alkaline, deionized water is used for washing to be neutral, and the extracted liquid enters an activated carbon decoloration filter column to remove yellow substances. Toluene and a small amount of water were removed by rotary evaporation at 55℃to give bis (pentafluorophenyl) pentafluorophenyl phosphonate as a white powder, molecular weight 580.15, yield 97.5%, acid number 0.018mgKOH/g.
Example 2
The preparation method of the pentafluorophenyl phosphonic acid di (pentafluorophenyl) ester flame retardant in the embodiment specifically comprises the following steps:
(1) Preparation of pentafluorophenyl phosphine dichloride:
Adding 4.8g of magnesium powder and 172.9g of tetrahydrofuran into a 500mL reactor, introducing nitrogen, stirring, heating to 57.5 ℃, slowly dripping 49.4g of pentafluorophenyl bromobenzene, setting the reaction time to 7 hours, obtaining pentafluorophenyl magnesium bromide after the reaction is finished, slowly adding 50g of phosphorus trichloride, gradually heating to 75 ℃, carrying out reflux reaction for 9 hours, removing salt by suction filtration, and then distilling to remove tetrahydrofuran and redundant phosphorus trichloride to obtain pentafluorophenyl phosphine dichloride with the molecular weight of 233.49;
(2) Preparation of pentafluorophenyl phosphonic dichloride:
Adding 46.7g of pentafluorophenyl phosphine dichloride and 95g of anhydrous phenylphosphonic acid into a 500mL reactor, introducing nitrogen, stirring, heating to 200 ℃, slowly introducing pure oxygen, observing reflux condition, ending the reaction after 5 hours, and evaporating the phenylphosphonic acid under reduced pressure to obtain pentafluorophenyl phosphonodichloride with molecular weight of 284.93;
(3) Preparation of bis (pentafluorophenyl) pentafluorophenyl phosphonate:
In a 500mL reactor, 57.0g of pentafluorophenyl phosphonyl dichloride, 95g of pentafluorophenol, 4g of anhydrous magnesium chloride and 145g of benzene are added, nitrogen is introduced and stirred, the temperature is increased to 140 ℃, the reflux reaction is carried out for 6 hours, hydrogen chloride gas generated in the process is carried into a sodium hydroxide solution sealer by the nitrogen through a tail pipe, after the reaction is finished, solid catalyst in liquid is removed by suction filtration, solvent benzene and superfluous pentafluorophenol are distilled off under reduced pressure, thus obtaining a crude product of bis (pentafluorophenyl) pentafluorophenyl phosphonate, 250g of benzene is added to dissolve bis (pentafluorophenyl) pentafluorophenyl phosphonate, 2% aqueous solution of potassium carbonate is used for washing to be alkaline, deionized water is used for washing to be neutral, and the extracted liquid enters an activated carbon decoloration filter column to remove yellow substances. Toluene and a small amount of water were removed by rotary evaporation at 55℃to give bis (pentafluorophenyl) pentafluorophenyl phosphonate as a white powder, molecular weight 580.15, yield 95.4%, acid number 0.023mgKOH/g.
Example 3
The preparation method of the pentafluorophenyl phosphonic acid di (pentafluorophenyl) ester flame retardant in the embodiment specifically comprises the following steps:
(1) Preparation of pentafluorophenyl phosphine dichloride:
adding 5.04g of magnesium powder and 251.94g of tetrahydrofuran into a 500mL reactor, introducing nitrogen, stirring, heating to 65 ℃, slowly dripping 49.4g of pentafluorobromide benzene, setting the reaction time to 8 hours, obtaining pentafluorophenyl magnesium bromide after the reaction is finished, slowly adding 50g of phosphorus trichloride, gradually heating to 81 ℃, carrying out reflux reaction for 7 hours, removing salt by suction, and distilling to remove tetrahydrofuran and redundant phosphorus trichloride to obtain pentafluorophenyl phosphine dichloride with the molecular weight of 233.49;
(2) Preparation of pentafluorophenyl phosphonic dichloride:
Adding 46.7g of pentafluorophenyl phosphine dichloride and 175g of anhydrous phenylphosphonic acid into a 500mL reactor, introducing nitrogen, stirring, heating to 225 ℃, slowly introducing pure oxygen, observing reflux condition, ending the reaction after 7 hours, and evaporating the phenylphosphonic acid under reduced pressure to obtain pentafluorophenyl phosphonodichloride with molecular weight of 284.93;
(3) Preparation of bis (pentafluorophenyl) pentafluorophenyl phosphonate:
In a 500mL reactor, 57.0g of pentafluorophenyl phosphonyl dichloride, 92g of pentafluorophenol, 4g of anhydrous zinc chloride and 200g of xylene are added, nitrogen is introduced and stirred, the temperature is increased to 175 ℃, reflux reaction is carried out for 4.5 hours, hydrogen chloride gas generated in the process is carried into a sodium hydroxide solution sealer by nitrogen through a tail pipe, after the reaction is finished, solid catalyst in liquid is removed by suction filtration, solvent xylene and superfluous pentafluorophenol are distilled off under reduced pressure, so that a crude product of bis (pentafluorophenyl) pentafluorophenyl phosphonate is obtained, 250g of xylene is added to dissolve bis (pentafluorophenyl) pentafluorophenyl phosphonate, 5% potassium carbonate aqueous solution is used for washing to be slightly alkaline, deionized water is used for washing to be neutral, and the extracted 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 ℃ to obtain white powder of pentafluorophenyl phosphonic acid di (pentafluorophenyl) ester, wherein the molecular weight is 580.15, the yield is 98.5 percent, and the acid value is 0.021mgKOH/g.
Example 4
The preparation method of the pentafluorophenyl phosphonic acid di (pentafluorophenyl) ester flame retardant in the embodiment specifically comprises the following steps:
(1) Preparation of pentafluorophenyl phosphine dichloride: step (1) is the same as in example 1;
(2) Preparation of pentafluorophenyl phosphonic dichloride: step (2) is the same as in example 1;
(3) Preparation of bis (pentafluorophenyl) pentafluorophenyl phosphonate:
In a 500mL reactor, 57.0g of pentafluorophenyl phosphonodichloride, 82g of pentafluorophenol, 4.5g of anhydrous magnesium bromide, 250g of toluene, stirring while introducing nitrogen, raising the temperature to 160 ℃, and carrying hydrogen chloride gas generated in the process to a sodium hydroxide solution sealer through a tail pipe by nitrogen, were added. After the reaction is finished, removing a solid catalyst in the liquid by suction filtration, removing solvent toluene and redundant pentafluorophenol by reduced pressure distillation to obtain a crude product of bis (pentafluorophenyl) pentafluorophosphonate, adding 250g of toluene to dissolve bis (pentafluorophenyl) pentafluorophenyl phosphonate, washing to be slightly alkaline by using a 5% potassium carbonate aqueous solution, washing to be neutral by using deionized water, and introducing the extracted liquid into an activated carbon decoloration filter column to remove yellow substances. Toluene and a small amount of water were removed by rotary evaporation at 55℃to give bis (pentafluorophenyl) pentafluorophenyl phosphonate as a white powder, molecular weight 580.15, yield 96.8%, acid number 0.016mgKOH/g.
Test example 1
Control 1: dimethyl methylphosphonate (DMMP);
Control 2: novel phosphorus-silicon flame retardants containing fluorophenyl groups and phosphate structures were prepared as in example 1 of CN 104725668A;
test samples 1-4 are bis (pentafluorophenyl) pentafluorophenyl phosphonate prepared in examples 1-4.
Different PMMA samples were prepared from control 1-2 and test 1-4 at a ratio of 40% with methyl methacrylate initiated with 0.1% ammonium persulfate initiator, and were designated as control 1-2 and test 1-4, respectively.
(1) Flame retardancy test
The limiting oxygen index of PMMA samples was measured by referring to GB/T2406-2008 "method for testing Plastic Combustion Performance-oxygen index method", and the results are shown in Table 1.
TABLE 1
LOI 28 is the limiting oxygen index of flame retardance, and as can be seen from Table 1, the PMMA samples prepared with the flame retardant of the present invention are significantly better in flame retardance than control sample 1 and control sample 2.
(2) Heat resistance test
Vicat softening points of PMMA samples were measured with reference to GB/T1633-2000 determination of thermoplastic Vicat Softening Temperature (VST), the results are shown in Table 2.
TABLE 2
It can be seen from Table 2 that PMMA samples prepared using the flame retardant of the present invention have significantly better heat resistance than control samples 1 and 2.
(3) Test for Water repellency
The contact angle of PMMA samples was measured with reference to GB/T30693-2014 measurement of contact angle of Plastic film with Water, and the results are shown in Table 3.
TABLE 3 Table 3
As can be seen from Table 3, PMMA samples prepared using the flame retardant of the present invention were significantly more water repellent than control samples 1 and 2.
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 (10)
1. A method for preparing a bis (pentafluorophenyl) pentafluorophenyl phosphonate flame retardant, the method comprising the steps of:
(1) Preparation of pentafluorophenyl phosphine dichloride: carrying out Grignard reaction on pentafluorobromide and magnesium powder in tetrahydrofuran to generate pentafluorophenyl magnesium bromide, and adding phosphorus trichloride into the pentafluorophenyl magnesium bromide to react to generate pentafluorophenyl phosphine dichloride;
(2) Preparation of pentafluorophenyl phosphonic dichloride: the pentafluorophenyl phosphorus dichloride is subjected to oxidation reaction under phenylphosphonic acid to obtain pentafluorophenyl phosphono dichloride;
(3) Preparation of bis (pentafluorophenyl) pentafluorophenyl phosphonate: the pentafluorophenyl phosphonic dichloride and the pentafluorophenyl phenol are subjected to esterification reaction in a catalyst and a solvent, and the pentafluorophenyl phosphonic acid di (pentafluorophenyl) ester is obtained through alkali washing, water washing, separation, color removal and distillation.
2. The method for preparing a bis (pentafluorophenyl) pentafluorophenyl phosphonate as in claim 1, wherein the grignard reaction temperature in step (1) is 50-65 ℃ and the reaction time is 7-8 hours.
3. The method for preparing the bis (pentafluorophenyl) pentafluorophenyl phosphonate flame retardant of claim 1, wherein the mass ratio of pentafluorophenyl to tetrahydrofuran in step (1) is 100:350-510, wherein the molar ratio of the pentafluorobromobenzene to the magnesium powder is 1:1-1.05, and the molar ratio of the pentafluorophenyl magnesium bromide to the phosphorus trichloride is 1:1.2-1.5.
4. A process for the preparation of bis (pentafluorophenyl) pentafluorophosphonate flame retardant as in claim 1 or 3, wherein in step (1) the reaction temperature of the pentafluorophenyl magnesium bromide and phosphorus trichloride is 75-81 ℃ and the reaction time is 7-9 hours.
5. The method for preparing the bis (pentafluorophenyl) pentafluorophosphonate flame retardant of claim 1, wherein the high temperature oxidation reaction temperature in step (2) is 200-250 ℃ and the reaction time is 5-7 hours, and the mass ratio of pentafluorophenyl phosphorus dichloride to phenylphosphonic acid is 100:200-550.
6. The method for preparing a bis (pentafluorophenyl) pentafluorophosphonate flame retardant of claim 1, wherein the molar ratio of pentafluorophenyl phosphonyl dichloride to pentafluorophenyl phenol in step (3) is 1:2-2.6 and the mass ratio of the total mass of pentafluorophenyl phosphonyl dichloride and pentafluorophenyl phenol to the catalyst is 100:2-5.
7. The method for preparing the bis (pentafluorophenyl) pentafluorophosphonate flame retardant of claim 1, wherein the solvent in step (3) is one of benzene, toluene and xylene, and the mass ratio of pentafluorophenyl phosphonyl dichloride to solvent is 100:250-440.
8. The method for preparing a bis (pentafluorophenyl) pentafluorophosphonate flame retardant of claim 1, wherein the catalyst in step (3) is one of anhydrous magnesium trichloride, anhydrous aluminum trichloride, anhydrous zinc trichloride, and anhydrous magnesium bromide.
9. The method for preparing the bis (pentafluorophenyl) pentafluorophosphonate flame retardant of claim 1, wherein in step (3), the alkaline washing is performed by using 2-8% by mass of aqueous potassium carbonate solution, and the color removal is performed by using an activated carbon leaching column.
10. A bis (pentafluorophenyl) pentafluorophenyl phosphonate flame retardant produced by the process of any of claims 1-9.
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| GB985650A (en) * | 1960-09-09 | 1965-03-10 | Imp Smelting Corp Ltd | Novel pentafluorophenyl-substituted alcohols |
| US3350412A (en) * | 1963-08-26 | 1967-10-31 | Du Pont | Process for the preparation of a pentafluorophenylmagnesium chloride-tetrahydrofuran complex |
| GB1376381A (en) * | 1971-05-20 | 1974-12-04 | Stauffer Chemical Co | Flame retardant phosphonate esters |
| CN104725668A (en) * | 2015-03-10 | 2015-06-24 | 三峡大学 | Fluorophenyl and phosphate structure-containing novel phosphorus-silicon flame retardant and preparation method and application thereof |
| CN104926875A (en) * | 2015-07-07 | 2015-09-23 | 苏州科技学院 | Flame retardant hydroxymethyl phosphonyl heterocyclic phenylphosphonate compound and preparation method therefor |
| CN106588577A (en) * | 2015-10-19 | 2017-04-26 | 江苏福瑞生物医药有限公司 | Pentafluorophenol synthesis method |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB985650A (en) * | 1960-09-09 | 1965-03-10 | Imp Smelting Corp Ltd | Novel pentafluorophenyl-substituted alcohols |
| US3350412A (en) * | 1963-08-26 | 1967-10-31 | Du Pont | Process for the preparation of a pentafluorophenylmagnesium chloride-tetrahydrofuran complex |
| GB1376381A (en) * | 1971-05-20 | 1974-12-04 | Stauffer Chemical Co | Flame retardant phosphonate esters |
| CN104725668A (en) * | 2015-03-10 | 2015-06-24 | 三峡大学 | Fluorophenyl and phosphate structure-containing novel phosphorus-silicon flame retardant and preparation method and application thereof |
| CN104926875A (en) * | 2015-07-07 | 2015-09-23 | 苏州科技学院 | Flame retardant hydroxymethyl phosphonyl heterocyclic phenylphosphonate compound and preparation method therefor |
| CN106588577A (en) * | 2015-10-19 | 2017-04-26 | 江苏福瑞生物医药有限公司 | Pentafluorophenol synthesis method |
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