CN111363397A - Vinyl phosphate flame retardant and preparation method thereof - Google Patents
Vinyl phosphate flame retardant and preparation method thereof Download PDFInfo
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- CN111363397A CN111363397A CN201811595000.5A CN201811595000A CN111363397A CN 111363397 A CN111363397 A CN 111363397A CN 201811595000 A CN201811595000 A CN 201811595000A CN 111363397 A CN111363397 A CN 111363397A
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- flame retardant
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- vinyl phosphate
- catalyst
- acrylate
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 46
- 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 44
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical compound OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 16
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 claims abstract description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 hydroxyalkyl ester Chemical class 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002274 desiccant Substances 0.000 claims description 5
- 239000003599 detergent Substances 0.000 claims description 5
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- INRQKLGGIVSJRR-UHFFFAOYSA-N 5-hydroxypentyl prop-2-enoate Chemical compound OCCCCCOC(=O)C=C INRQKLGGIVSJRR-UHFFFAOYSA-N 0.000 claims description 2
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- 239000012266 salt solution Substances 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 235000017168 chlorine Nutrition 0.000 abstract description 3
- 125000001309 chloro group Chemical class Cl* 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 3
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- RBKRNMZZYQWTJL-UHFFFAOYSA-N 1,2-dichlorobenzene phosphoric acid Chemical compound P(=O)(O)(O)O.ClC1=C(C=CC=C1)Cl RBKRNMZZYQWTJL-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- 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
- C07F9/4075—Esters with hydroxyalkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a vinyl phosphate flame retardant, which is phenylphosphoalkene ester prepared by using phenylphosphoryl dichloride and alkyl acrylate in a solvent such as dichloromethane, diethyl ether or tetrahydrofuran and the like under the action of a catalyst triethylamine or pyridine to generate a final target product, namely phenylphosphoryl dichloride, wherein two chlorines of the phenylphosphoryl dichloride are disubstituted by the alkyl acrylate. The invention has the following advantages: does not contain halogen, is nontoxic, and is beneficial to environmental protection: the thermal stability is higher, and the char forming property is higher; the organic phosphorus flame retardant is a reactive organic phosphorus flame retardant, can be widely applied to preparation of various acrylic acid and acrylic ester flame retardant coating emulsions, and cannot influence the performances of the coating such as adhesive force, weather resistance and the like after being added into the coating; high flame-retardant effect can be achieved under the condition of small addition amount in the coating.
Description
Technical Field
The invention relates to the field of flame retardants, in particular to a vinyl phosphate flame retardant containing a phosphorus-containing vinyl monomer and a preparation method thereof.
Background
The acrylate emulsion has been widely used as a film forming base material of a water-based coating material due to the characteristics of excellent film forming property, flexibility, environmental protection and the like, and is applied to the technical fields of coatings, adhesives, textile printing and dyeing, daily chemical industry and the like. However, acrylate polymers are extremely flammable, which severely limits their use in areas where flame retardancy is a requirement. The additive type flame retardant is generally added in a larger amount, and the compatibility of the added flame retardant and the emulsion is poor, so that the performance of the emulsion and the mechanical property and appearance of the prepared coating are greatly influenced. Therefore, the preparation of the reactive flame-retardant acrylate has a great development prospect, and can play a very high flame-retardant effect on the premise of a small addition amount, so that the technology is urgently needed in the current market. However, the prior art documents have not disclosed a solution to the above-mentioned problems for a while.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a vinyl phosphate flame retardant.
Another object of the present invention is to provide a method for preparing a vinyl phosphate flame retardant.
In order to realize the purpose of the invention, the invention adopts the technical scheme that: a flame-retarding agent of vinyl phosphate is prepared from phenylphosphoryl dichloride and hydroxyalkyl ester through dissolving them in solvent and reaction under the action of catalyst.
The hydroxyalkyl ester is one or the combination of more than two of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate and/or 3-hydroxypropyl methacrylate.
The solvent is one or the combination of more than two of dichloromethane, trichloromethane, tetrahydrofuran or diethyl ether.
The catalyst is triethylamine or pyridine.
A preparation method of a vinyl phosphate flame retardant comprises the following steps: the method comprises the steps of dissolving phenylphosphoryl dichloride and hydroxyalkyl ester in a solvent, reacting under the action of a catalyst, and purifying to obtain a disubstituted target product vinyl phosphate with two chlorines of the phenylphosphoryl dichloride substituted by the hydroxyalkyl ester.
Preferably, the preparation method of the vinyl phosphate flame retardant comprises the following steps: adding phenylphosphoryl dichloride and a catalyst into a solvent in a container, dropwise adding hydroxyalkyl ester dissolved in the solvent at 0-20 ℃, after dropwise adding, heating to 25-50 ℃, reacting for 6-12 hours, and when no HCl is discharged, finishing the reaction; evaporating the product to remove the solvent, washing for 1-5 times by using a detergent, drying for 8-15 hours by using a drying agent, and finally performing suction filtration to obtain colorless liquid, namely the target product vinyl phosphate.
Preferably, the preparation method of the vinyl phosphate flame retardant comprises the following steps: adding phenylphosphoryl dichloride and a catalyst into a solvent in a four-opening container provided with a nitrogen inlet and a nitrogen outlet and a stirring rotor, slowly dripping hydroxyalkyl ester dissolved in the solvent under stirring at the low temperature of 5-10 ℃ (the rotating speed is 50-150rmp), after finishing dripping, raising the temperature to 30-40 ℃, reacting for 8-10 hours, and when no HCl is discharged, finishing the reaction; and rotationally evaporating the product in a rotary evaporator for 20-40 minutes to remove the solvent, washing for 3 times by using a detergent, drying for 12 hours by using a drying agent, and finally performing suction filtration to obtain colorless liquid, namely the target product vinyl phosphate.
The molar ratio of the phenylphosphoryl dichloride to the hydroxyalkyl ester is 1: 2 to 5.
The dosage of the catalyst triethylamine is equal to the molar quantity of the hydroxyalkyl ester.
The addition amount of the solvent is 5-50 times of the mass of the phenylphosphoryl dichloride or the hydroxyalkyl ester.
The detergent is water or saturated salt water.
The drying agent is one of anhydrous magnesium sulfate or anhydrous calcium chloride.
Compared with the prior art, the invention has the following advantages:
(1) the flame retardant does not contain halogen, is nontoxic, is beneficial to environmental protection, has good application prospect, and also adds a new variety for the phosphorus-containing vinyl flame retardant;
(2) the flame retardant is a reactive flame retardant, has higher thermal stability and higher char formation, can be polymerized with acrylic ester and the like to form an intrinsic flame retardant polymer, can be added in a small amount and has a high flame retardant effect;
(3) the preparation method is simple and easy to operate.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The invention relates to a vinyl phosphate flame retardant, which is phenyl phosphoroalkylene ester of which two chlorines of benzene phosphoryl dichloride are disubstituted by alkyl acrylate and is the final target product of benzene phosphoryl dichloride generated under the action of catalyst triethylamine or pyridine in a solvent of methylene dichloride, diethyl ether or tetrahydrofuran. The molar ratio of the phenylphosphoryl dichloride to the hydroxyalkyl ester is 1: 3 to 4. The dosage of the catalyst triethylamine is equal to the molar quantity of the hydroxyalkyl ester.
Example 1
A preparation method of a vinyl phosphate flame retardant comprises the following steps: in a 500ml four-mouth flask provided with a nitrogen inlet and a nitrogen outlet and a stirring rotor, 9.82g of phenylphosphoryl dichloride and 0.105mol of pyridine are added into 80ml of dichloromethane as catalysts, 13.66g of hydroxyethyl methacrylate dissolved in 80ml of dichloromethane are dropwise added within 1 hour under the condition of slow stirring at 0 ℃, after the dropwise addition is finished, the temperature is raised to 30 ℃, and then the reaction is carried out for 8 hours, namely no HCl is discharged, and the reaction is finished; and standing, carrying out rotary evaporation on the product in a rotary evaporator for 25 minutes to remove the solvent, washing the residual product after distillation with saturated saline solution for three times, drying with anhydrous magnesium sulfate for 12 hours, and finally carrying out suction filtration to obtain colorless liquid, namely the target product vinyl phosphate, wherein the yield is 91 percent.
Example 2
A preparation method of a vinyl phosphate flame retardant comprises the following steps: in a 500ml four-necked flask equipped with a nitrogen inlet/outlet and a stirring rotor, 9.82g of dichlorbenzene phosphate and 0.105mol of pyridine as catalysts were added to 80ml of diethyl ether, and 12.19g of 2-hydroxyethyl acrylate dissolved in 80ml of diethyl ether was dropwise added at 10 ℃ under slow stirring over 1 hour, and after completion of the dropwise addition, the temperature was raised to 35 ℃. Then reacting for 10 hours until no HCl is released, and finishing the reaction; and standing, carrying out rotary evaporation on the product in a rotary evaporator for 30 minutes to remove the solvent, washing the residual product after distillation with saturated saline solution for three times, drying with anhydrous magnesium sulfate for 10 hours, and finally carrying out suction filtration to obtain colorless liquid, namely the target product vinyl phosphate, wherein the yield is 87 percent.
Example 3
A preparation method of a vinyl phosphate flame retardant comprises the following steps: in a 500ml four-mouth flask provided with a nitrogen inlet and a nitrogen outlet and a stirring rotor, 11.20g of phenylphosphoryl dichloride and 0.21mol of triethylamine are added into 80ml of tetrahydrofuran as catalysts, 30.28g of 2-hydroxypropyl methacrylate dissolved in 100ml of tetrahydrofuran is dropwise added at 15 ℃ within 1 hour under slow stirring, after the dropwise addition is finished, the temperature is raised to 50 ℃, and then the reaction is carried out for 8 hours until no HCl is discharged, and the reaction is finished; standing, carrying out rotary evaporation on the product in a rotary evaporator for 39 minutes to remove the solvent, washing the residual product after distillation with saturated saline solution for three times, then drying with anhydrous calcium chloride for 13 hours, and finally carrying out suction filtration to obtain colorless liquid, namely the target product vinyl phosphate, wherein the yield is 85 percent.
Example 4
A preparation method of a vinyl phosphate flame retardant comprises the following steps: in a 500ml four-mouth flask provided with a nitrogen inlet and a nitrogen outlet and a stirring rotor, 11.20g of phenylphosphoryl dichloride and 0.18mol of triethylamine are added into 80ml of tetrahydrofuran as catalysts, 25.95g of 2-hydroxypropyl methacrylate dissolved in 100ml of tetrahydrofuran is dropwise added at 8 ℃ within 1 hour under slow stirring, the temperature is raised to 45 ℃ after the dropwise addition is finished, then the reaction is carried out for 8 hours, and the reaction is finished after no HCl is discharged; standing, carrying out rotary evaporation on the product in a rotary evaporator for 35 minutes to remove the solvent, washing the residual product after distillation with saturated saline solution for three times, then drying with anhydrous calcium chloride for 12 hours, and finally carrying out suction filtration to obtain colorless liquid, namely the target product vinyl phosphate, wherein the yield is 85 percent.
The vinyl phosphate flame retardant is added into the acrylate emulsion, the addition amount is 5-15% of the total mass, and the preferred addition amount is 10%. The flame retardant acrylate emulsion prepared by polymerizing the vinyl phosphate flame retardant, the alkyl methacrylate, the alkyl acrylate and the like has obviously improved flame retardant performance, and the horizontal and vertical combustion test of L94 reaches V-0 level. According to the flame-retardant acrylate emulsion prepared by emulsion polymerization of the vinyl phosphate flame retardant, methyl methacrylate and butyl acrylate monomers (the polymerization process can refer to the Chinese invention patent application publication with the application number of 201410372753.5), when the addition amount of the vinyl phosphate flame retardant is 10%, the Limiting Oxygen Index (LOI) of the obtained flame-retardant acrylate emulsion reaches 29.8%, the LOI is increased by 10.8% compared with the LOI of a polymer without the flame-retardant monomer (the LOI of a methyl methacrylate and butyl acrylate copolymer is 17.8%), the UL94 horizontal vertical combustion test reaches the V-0 level, and the flame-retardant performance is remarkably improved. The invention has similar effect with the acrylic ester emulsion obtained by polymerizing other alkyl methacrylate and alkyl acrylate, and the flame retardant property is obviously improved.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention should not be limited thereby, and all the simple equivalent changes and modifications made in the claims and the description of the present invention are within the scope of the present invention.
Claims (10)
1. A vinyl phosphate flame retardant is characterized in that the flame retardant is prepared by dissolving benzene phosphoryl dichloride and hydroxyalkyl ester in a solvent and reacting under the action of a catalyst.
2. The method of claim 1, wherein the hydroxyalkyl ester is one or a combination of two or more of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate and/or 3-hydroxypropyl methacrylate.
3. The method for synthesizing vinyl phosphate ester flame retardant according to claim 1, wherein the solvent is one or a combination of two or more of dichloromethane, chloroform, tetrahydrofuran and diethyl ether.
4. The method for synthesizing the vinyl phosphate ester flame retardant as claimed in claim 1, wherein the catalyst is triethylamine or pyridine.
5. A method for preparing a vinyl phosphate flame retardant according to any of claims 1 to 5, comprising the steps of: the benzene phosphoryl dichloride and the hydroxyalkyl ester are dissolved in a solvent, react under the action of a catalyst and are purified.
6. The method for preparing a vinyl phosphate ester flame retardant according to claim 5, comprising the steps of: adding phenylphosphoryl dichloride and a catalyst into a solvent in a container, dropwise adding hydroxyalkyl ester dissolved in the solvent at 0-20 ℃, after dropwise adding, heating to 25-50 ℃, reacting for 6-12 hours, and when no HCl is discharged, finishing the reaction; evaporating the product to remove the solvent, washing with a detergent for 1-5 times, drying with a drying agent for 8-15 hours, and finally performing suction filtration.
7. The method of claim 6, wherein the molar ratio of the phenylphosphoryl dichloride to the hydroxyalkyl ester is 1: 2 to 5.
8. The method of claim 6, wherein the triethylamine catalyst is used in an amount equimolar to the hydroxyalkyl ester catalyst.
9. The method of claim 6, wherein the detergent is water or saturated salt solution.
10. The method of claim 6, wherein the drying agent is one of anhydrous magnesium sulfate or anhydrous calcium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811595000.5A CN111363397A (en) | 2018-12-25 | 2018-12-25 | Vinyl phosphate flame retardant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811595000.5A CN111363397A (en) | 2018-12-25 | 2018-12-25 | Vinyl phosphate flame retardant and preparation method thereof |
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| CN111363397A true CN111363397A (en) | 2020-07-03 |
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| CN201811595000.5A Pending CN111363397A (en) | 2018-12-25 | 2018-12-25 | Vinyl phosphate flame retardant and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007210901A (en) * | 2006-02-07 | 2007-08-23 | Songwon Industrial Co Ltd | Organic phosphorus compound, flame retardant and flame-retarding organic polymer composition |
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| CN107814860A (en) * | 2016-09-12 | 2018-03-20 | 华北理工大学 | A kind of polyacrylate fire retardant of phosphorus-nitrogen containing silicon and preparation method thereof |
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| JP2007210901A (en) * | 2006-02-07 | 2007-08-23 | Songwon Industrial Co Ltd | Organic phosphorus compound, flame retardant and flame-retarding organic polymer composition |
| CN101497630A (en) * | 2009-03-09 | 2009-08-05 | 安徽恒远化工有限公司 | Phosphoric acrylic ester monomer, hyperbranched polymer flame retardant and preparation thereof |
| CN107814860A (en) * | 2016-09-12 | 2018-03-20 | 华北理工大学 | A kind of polyacrylate fire retardant of phosphorus-nitrogen containing silicon and preparation method thereof |
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