CN111675785A - Ferrocene-organophosphorus reactive flame retardant modified acrylic resin and preparation method thereof - Google Patents
Ferrocene-organophosphorus reactive flame retardant modified acrylic resin and preparation method thereof Download PDFInfo
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- CN111675785A CN111675785A CN202010658915.7A CN202010658915A CN111675785A CN 111675785 A CN111675785 A CN 111675785A CN 202010658915 A CN202010658915 A CN 202010658915A CN 111675785 A CN111675785 A CN 111675785A
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- ferrocene
- organophosphorus
- flame retardant
- beta
- cyclodextrin
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 74
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 34
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 7
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 61
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 61
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 61
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 61
- 229960004853 betadex Drugs 0.000 claims abstract description 61
- 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 claims abstract description 42
- -1 diformyl chloride Chemical compound 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 27
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 16
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 16
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims description 68
- 238000006243 chemical reaction Methods 0.000 claims description 56
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 16
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 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 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000003125 aqueous solvent Substances 0.000 claims 1
- LDSUEKXPKCHROT-UHFFFAOYSA-N cyclopenta-1,3-diene-1-carboxylic acid;iron(2+) Chemical compound [Fe+2].OC(=O)C1=CC=C[CH-]1.OC(=O)C1=CC=C[CH-]1 LDSUEKXPKCHROT-UHFFFAOYSA-N 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 239000000779 smoke Substances 0.000 abstract description 3
- 150000001263 acyl chlorides Chemical group 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000000979 retarding effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 239000012265 solid product Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000002604 ultrasonography Methods 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to the technical field of acrylic resin flame retardance and discloses a ferrocene-organophosphorus reactive flame retardant modified acrylic resin, wherein a unique cavity structure of beta-cyclodextrin has good inclusion effect on 1,1 '-ferrocene diformyl chloride, an acyl chloride group of the 1,1' -ferrocene diformyl chloride reacts with an active phenolic hydroxyl group of 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to obtain a beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant, ammonium ceric nitrate is used as an initiator to initiate in-situ polymerization of a beta-cyclodextrin component and monomers such as methyl methacrylate and the like, so that the beta-cyclodextrin coated ferrocene-organophosphorus is used as a reactive flame retardant, the ferrocene-organophosphorus polymer is added into a molecular chain of acrylic resin, has little influence on the mechanical property and the service performance of the material, and has good functions of inhibiting smoke, promoting carbon formation and retarding flame by being used as a flame-retardant active component.
Description
Technical Field
The invention relates to the technical field of acrylic resin flame retardance, in particular to ferrocene-organophosphorus reactive flame retardant modified acrylic resin and a preparation method thereof.
Background
The functional assistant for improving the flame retardance and the flame resistance of materials such as organic polymers and the like by the flame retardant can be divided into an additive flame retardant and a reactive flame retardant, wherein the reactive flame retardant is added into polymer molecules as a polymerization monomer, has more lasting flame retardance than the additive flame retardant, and has smaller influence on the mechanical property and the service performance of a high polymer material.
The fire retardant mainly comprises a brominated fire retardant, a phosphorus fire retardant, a nitrogen-phosphorus fire retardant and the like, ferrocene is a metal organic compound and has certain effects of inhibiting smoke and promoting carbon formation, the organic phosphorus fire retardant such as 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like is a novel fire retardant intermediate, and a molecular structure contains a biphenyl structure and a phenanthrene ring structure, so that the chemical stability and the thermal stability are higher, and the fire retardant performance is more excellent.
The acrylate resin is a common synthetic high molecular polymer, has good weather resistance, solvent resistance, adhesive property and electrical insulation property, and can be widely applied to the fields of coatings, adhesives, printing ink and the like, but the thermal stability and flame retardant property of the acrylate resin are poor, so that the application range of the acrylate resin material is limited, and compared with an additive flame retardant, the use of a reactive flame retardant is more beneficial to the flame retardant property of the acrylate resin material, and the influence on the service performance of the material is small.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the efficient ferrocene-organic phosphorus reaction type flame retardant modified acrylic resin and the preparation method thereof, solves the problem of poor flame retardance of the acrylate resin, and simultaneously solves the problem that the additive type flame retardant can influence the service performance of the acrylate resin.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a ferrocene-organophosphorus reactive flame retardant modified acrylic resin: the preparation method of the ferrocene-organophosphorus reactive flame retardant modified acrylic resin comprises the following steps:
(1) adding a dichloromethane solvent, 1 '-ferrocene dicarboxylic acid with the mass ratio of 100:200 and 250:7-10, oxalyl chloride and pyridine into a reaction bottle, stirring at a constant speed at 20-30 ℃ for reaction for 6-18h under a dark condition, heating to 40-60 ℃, performing reflux reaction for 5-10h, performing reduced pressure distillation to remove the solvent, extracting and purifying by using a hot n-hexane solvent, and preparing the 1,1' -ferrocene diformyl chloride.
(2) Adding an anhydrous N, N-dimethylformamide solvent and beta-cyclodextrin into a reaction bottle, stirring uniformly at 60-80 ℃, adding 1,1 '-ferrocene diformyl chloride, stirring uniformly for reacting for 3-8h, drying the solution in vacuum to remove the solvent, washing a solid product by using tetrahydrofuran, and drying to prepare the beta-cyclodextrin coated 1,1' -ferrocene diformyl chloride.
(3) Adding a dichloromethane solvent and beta-cyclodextrin to coat 1,1' -ferrocene diformyl chloride into a reaction bottle in a nitrogen atmosphere, adding 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide after uniformly dispersing by ultrasonic wave, stirring at a constant speed to react, distilling the solution under reduced pressure to remove the solvent, washing a solid product by using methanol, and drying to prepare the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant.
(4) Adding a distilled water solvent and beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant into a reaction bottle, adding methyl methacrylate, acrylic acid and n-butyl acrylate after uniformly dispersing by ultrasound, slowly dropwise adding a ceric ammonium nitrate aqueous solution after uniformly stirring, stirring at a constant speed for reaction, filtering the solution to remove the solvent, washing with distilled water, and dialyzing to remove impurities to prepare the ferrocene-organophosphorus reactive flame retardant modified acrylic resin.
Preferably, the mass ratio of the beta-cyclodextrin to the 1,1' -ferrocene diformyl chloride in the step (2) is 8-15: 10.
Preferably, the mass ratio of the beta-cyclodextrin coated 1,1' -ferrocene diformyl chloride to the 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in the step (3) is 100: 40-70.
Preferably, the reaction temperature in the step (3) is 20-30 ℃, and the reaction time is 12-24 h.
Preferably, the mass ratio of the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant, the methyl methacrylate, the acrylic acid, the n-butyl acrylate and the cerium ammonium nitrate in the step (4) is 0.5-5:100:2-8: 5-15.
Preferably, the reaction temperature in the step (4) is 60-80 ℃, and the reaction time is 6-12 h.
(III) advantageous technical effects
Compared with the prior art, the invention has the following chemical mechanism and beneficial technical effects:
the ferrocene-organophosphorus reactive flame retardant modified acrylic resin has a unique cavity structure of beta-cyclodextrin, has good inclusion effect on 1,1 '-ferrocene diformyl chloride, the acyl chloride group of the 1,1' -ferrocene diformyl chloride reacts with the active phenolic hydroxyl of 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide under the action of triethylamine to obtain the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant, ammonium ceric nitrate is used as an initiator to initiate the in-situ polymerization of the beta-cyclodextrin component in the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant and monomers such as methyl methacrylate and the like, so that the beta-cyclodextrin coated ferrocene-organophosphorus is used as the reactive flame retardant, the ferrocene-organophosphorus polymer is used as a flame-retardant active component, has good effects of inhibiting smoke and promoting carbon formation, promotes the formation of a compact carbon layer on the surface of the material, is beneficial to external heat and oxygen to permeate into the material, and has an excellent flame-retardant effect.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples:
the preparation method of the ferrocene-organophosphorus reactive flame retardant modified acrylic resin comprises the following steps:
(1) adding a dichloromethane solvent, 1 '-ferrocene dicarboxylic acid with the mass ratio of 100:200 and 250:7-10, oxalyl chloride and pyridine into a reaction bottle, stirring at a constant speed at 20-30 ℃ for reaction for 6-18h under a dark condition, heating to 40-60 ℃, performing reflux reaction for 5-10h, performing reduced pressure distillation to remove the solvent, extracting and purifying by using a hot n-hexane solvent, and preparing the 1,1' -ferrocene diformyl chloride.
(2) Adding an anhydrous N, N-dimethylformamide solvent and beta-cyclodextrin into a reaction bottle, stirring uniformly at 60-80 ℃, adding 1,1 '-ferrocene diformyl chloride, wherein the mass ratio of the two is 8-15:10, stirring at a constant speed for reacting for 3-8h, drying the solution in vacuum to remove the solvent, washing a solid product by using tetrahydrofuran, and drying to prepare the beta-cyclodextrin coated 1,1' -ferrocene diformyl chloride.
(3) Adding a dichloromethane solvent and beta-cyclodextrin to coat 1,1' -ferrocene diformyl chloride into a reaction bottle in a nitrogen atmosphere, adding 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide after uniformly dispersing by ultrasonic, stirring at a constant speed for reaction for 12-24h at 20-30 ℃ with the mass ratio of 100:40-70, removing the solvent from the solution by reduced pressure distillation, washing a solid product by using methanol, and drying to prepare the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant.
(4) Adding a distilled water solvent and a beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant into a reaction bottle, adding methyl methacrylate, acrylic acid and n-butyl acrylate after uniformly dispersing by ultrasound, slowly dropwise adding an aqueous solution of ammonium ceric nitrate after uniformly stirring, controlling the mass ratio of the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant, the methyl methacrylate, the acrylic acid, the n-butyl acrylate and the ammonium ceric nitrate to be 0.5-5:100:2-8:5-15, reacting for 6-12h at a constant speed under the temperature of 60-80 ℃, filtering the solution to remove the solvent, washing with distilled water, dialyzing to remove impurities, and preparing the ferrocene-organophosphorus reactive flame retardant modified acrylic resin.
Example 1
(1) Adding a dichloromethane solvent, 1 '-ferrocene dicarboxylic acid, oxalyl chloride and pyridine in a mass ratio of 100:200:7 into a reaction bottle, reacting for 6 hours at a constant speed at 20 ℃ in a dark condition, heating to 40 ℃, performing reflux reaction for 5 hours, removing the solvent by reduced pressure distillation, extracting and purifying by using a hot n-hexane solvent, and preparing the 1,1' -ferrocene diformyl chloride.
(2) Adding an anhydrous N, N-dimethylformamide solvent and beta-cyclodextrin into a reaction bottle, stirring uniformly at 60 ℃, adding 1,1 '-ferrocene diformyl chloride, wherein the mass ratio of the two is 8:10, stirring at a constant speed for reaction for 3 hours, drying the solution in vacuum to remove the solvent, washing a solid product by using tetrahydrofuran, and drying to prepare the beta-cyclodextrin coated 1,1' -ferrocene diformyl chloride.
(3) Adding a dichloromethane solvent and beta-cyclodextrin to coat 1,1' -ferrocene diformyl chloride into a reaction bottle in a nitrogen atmosphere, adding 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide after uniformly dispersing by ultrasonic, stirring at a constant speed for reaction for 12 hours at 20 ℃ with the mass ratio of 100:40, removing the solvent by distilling the solution under reduced pressure, washing a solid product by using methanol and drying to prepare the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant.
(4) Adding a distilled water solvent and a beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant into a reaction bottle, adding methyl methacrylate, acrylic acid and n-butyl acrylate after uniformly dispersing by ultrasound, slowly dropwise adding an aqueous solution of ammonium ceric nitrate after uniformly stirring, controlling the mass ratio of the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant to the methyl methacrylate, the acrylic acid, the n-butyl acrylate and the ammonium ceric nitrate to be 0.5:100:2:5, stirring at a constant speed for reaction for 6 hours at 60 ℃, filtering the solution to remove the solvent, washing with distilled water and removing impurities by dialysis, thus obtaining the ferrocene-organophosphorus reactive flame retardant modified acrylic resin 1.
Example 2
(1) Adding a dichloromethane solvent, 1 '-ferrocene dicarboxylic acid, oxalyl chloride and pyridine in a mass ratio of 100:210:8 into a reaction bottle, reacting for 12 hours at 30 ℃ with uniform stirring in a dark condition, heating to 40 ℃, performing reflux reaction for 10 hours, removing the solvent by reduced pressure distillation, extracting and purifying by using a hot n-hexane solvent, and preparing the 1,1' -ferrocene diformyl chloride.
(2) Adding an anhydrous N, N-dimethylformamide solvent and beta-cyclodextrin into a reaction bottle, stirring uniformly at 80 ℃, adding 1,1 '-ferrocene diformyl chloride, wherein the mass ratio of the two is 10:10, stirring at a constant speed for reaction for 3 hours, drying the solution in vacuum to remove the solvent, washing a solid product by using tetrahydrofuran, and drying to prepare the beta-cyclodextrin coated 1,1' -ferrocene diformyl chloride.
(3) Adding a dichloromethane solvent and beta-cyclodextrin to coat 1,1' -ferrocene diformyl chloride into a reaction bottle in a nitrogen atmosphere, adding 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide after uniformly dispersing by ultrasonic, stirring at a constant speed for reaction for 18 hours at 30 ℃ with the mass ratio of 100:50, removing the solvent by distilling the solution under reduced pressure, washing a solid product by using methanol and drying to prepare the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant.
(4) Adding a distilled water solvent and a beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant into a reaction bottle, adding methyl methacrylate, acrylic acid and n-butyl acrylate after uniformly dispersing by ultrasound, slowly dropwise adding an aqueous solution of ammonium ceric nitrate after uniformly stirring, controlling the mass ratio of the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant to the methyl methacrylate, the acrylic acid, the n-butyl acrylate and the ammonium ceric nitrate to be 1.5:100:4:8, stirring at a constant speed for reaction for 12 hours at 60 ℃, filtering the solution to remove the solvent, washing with distilled water and removing impurities by dialysis, thus obtaining the ferrocene-organophosphorus reactive flame retardant modified acrylic resin 2.
Example 3
(1) Adding a dichloromethane solvent, 1 '-ferrocene dicarboxylic acid, oxalyl chloride and pyridine in a mass ratio of 100:230:8.5 into a reaction bottle, reacting for 12 hours at 25 ℃ with uniform stirring in a dark condition, heating to 50 ℃, refluxing for 8 hours, removing the solvent by reduced pressure distillation, extracting and purifying by using a hot n-hexane solvent, and preparing the 1,1' -ferrocene diformyl chloride.
(2) Adding an anhydrous N, N-dimethylformamide solvent and beta-cyclodextrin into a reaction bottle, stirring uniformly at 70 ℃, adding 1,1 '-ferrocene diformyl chloride, wherein the mass ratio of the two is 12:10, stirring at a constant speed for 5 hours, carrying out vacuum drying on the solution to remove the solvent, washing a solid product by using tetrahydrofuran, and drying to prepare the beta-cyclodextrin coated 1,1' -ferrocene diformyl chloride.
(3) Adding a dichloromethane solvent and beta-cyclodextrin to coat 1,1' -ferrocene diformyl chloride into a reaction bottle in a nitrogen atmosphere, adding 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide after uniformly dispersing by ultrasonic, stirring at a constant speed for reaction for 18 hours at 25 ℃ with the mass ratio of 100:60, removing the solvent by distilling the solution under reduced pressure, washing a solid product by using methanol and drying to prepare the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant.
(4) Adding a distilled water solvent and a beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant into a reaction bottle, adding methyl methacrylate, acrylic acid and n-butyl acrylate after uniformly dispersing by ultrasound, slowly dropwise adding an aqueous solution of ammonium ceric nitrate after uniformly stirring, controlling the mass ratio of the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant to the methyl methacrylate, the acrylic acid, the n-butyl acrylate and the ammonium ceric nitrate to be 3:100:6:12, carrying out uniform stirring reaction at 70 ℃ for 12 hours, filtering the solution to remove the solvent, washing with distilled water, dialyzing to remove impurities, and preparing the ferrocene-organophosphorus reactive flame retardant modified acrylic resin 3.
Example 4
(1) Adding a dichloromethane solvent, 1 '-ferrocene dicarboxylic acid, oxalyl chloride and pyridine in a mass ratio of 100:250:10 into a reaction bottle, reacting for 18 hours at 30 ℃ under constant stirring in a dark condition, heating to 60 ℃, performing reflux reaction for 10 hours, removing the solvent by reduced pressure distillation, extracting and purifying by using a hot n-hexane solvent, and preparing the 1,1' -ferrocene diformyl chloride.
(2) Adding an anhydrous N, N-dimethylformamide solvent and beta-cyclodextrin into a reaction bottle, stirring uniformly at 80 ℃, adding 1,1 '-ferrocene diformyl chloride, wherein the mass ratio of the two is 15:10, stirring at a constant speed for reacting for 8 hours, drying the solution in vacuum to remove the solvent, washing a solid product by using tetrahydrofuran, and drying to prepare the beta-cyclodextrin coated 1,1' -ferrocene diformyl chloride.
(3) Adding a dichloromethane solvent and beta-cyclodextrin to coat 1,1' -ferrocene diformyl chloride into a reaction bottle in a nitrogen atmosphere, adding 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide after uniformly dispersing by ultrasonic, stirring at a constant speed for reaction for 24 hours at 30 ℃ with the mass ratio of 100:70, removing the solvent by distilling the solution under reduced pressure, washing a solid product by using methanol and drying to prepare the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant.
(4) Adding a distilled water solvent and a beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant into a reaction bottle, adding methyl methacrylate, acrylic acid and n-butyl acrylate after uniformly dispersing by ultrasound, slowly dropwise adding an aqueous solution of ammonium ceric nitrate after uniformly stirring, controlling the mass ratio of the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant to the methyl methacrylate, the acrylic acid, the n-butyl acrylate and the ammonium ceric nitrate to be 5:100:8:15, uniformly stirring and reacting for 12 hours at 80 ℃, filtering the solution to remove the solvent, washing with distilled water and dialyzing to remove impurities, thus preparing the ferrocene-organophosphorus reactive flame retardant modified acrylic resin 4.
Comparative example 1
(1) Adding a dichloromethane solvent, 1 '-ferrocene dicarboxylic acid, oxalyl chloride and pyridine in a mass ratio of 100:180:6 into a reaction bottle, reacting for 18 hours at a constant speed at 30 ℃ in a dark condition, heating to 50 ℃, performing reflux reaction for 5 hours, removing the solvent by reduced pressure distillation, extracting and purifying by using a hot n-hexane solvent, and preparing the 1,1' -ferrocene diformyl chloride.
(2) Adding an anhydrous N, N-dimethylformamide solvent and beta-cyclodextrin into a reaction bottle, stirring uniformly at 70 ℃, adding 1,1 '-ferrocene diformyl chloride, wherein the mass ratio of the two is 6:10, stirring at a constant speed for reacting for 3-8h, drying the solution in vacuum to remove the solvent, washing a solid product by using tetrahydrofuran, and drying to prepare the beta-cyclodextrin coated 1,1' -ferrocene diformyl chloride.
(3) Adding a dichloromethane solvent and beta-cyclodextrin to coat 1,1' -ferrocene diformyl chloride into a reaction bottle in a nitrogen atmosphere, adding 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide after uniformly dispersing by ultrasonic, stirring at a constant speed for reaction for 18 hours at the temperature of 30 ℃ at a mass ratio of 100:30, removing the solvent by distilling the solution under reduced pressure, washing a solid product by using methanol, and drying to prepare the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant.
(4) Adding a distilled water solvent and a beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant into a reaction bottle, adding methyl methacrylate, acrylic acid and n-butyl acrylate after uniformly dispersing by ultrasound, slowly dropwise adding an aqueous solution of ammonium ceric nitrate after uniformly stirring, controlling the mass ratio of the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant to the methyl methacrylate, the acrylic acid, the n-butyl acrylate and the ammonium ceric nitrate to be 0.2:100:5:12, stirring at a constant speed for reaction for 12 hours at 70 ℃, filtering the solution to remove the solvent, washing with distilled water and removing impurities by dialysis, thus obtaining the ferrocene-organophosphorus reactive flame retardant modified acrylic resin comparative 1.
The limiting oxygen indexes of the ferrocene-organophosphorus reactive flame retardant modified acrylic resin in the examples and the comparative examples are tested by using a GB2406 limiting oxygen index tester, and the test standard is GB/T2406.1-2008.
Claims (6)
1. A ferrocene-organophosphorus reactive flame retardant modified acrylic resin is characterized in that: the preparation method of the ferrocene-organophosphorus reactive flame retardant modified acrylic resin comprises the following steps:
(1) adding 1,1 '-ferrocene dicarboxylic acid, oxalyl chloride and pyridine in a mass ratio of 100:200 and 250:7-10 into a dichloromethane solvent, reacting for 6-18h at 20-30 ℃ under a dark condition, heating to 40-60 ℃, performing reflux reaction for 5-10h, and performing reduced pressure distillation and purification to prepare 1,1' -ferrocene diformyl chloride;
(2) adding beta-cyclodextrin into an anhydrous N, N-dimethylformamide solvent, adding 1,1 '-ferrocene diformyl chloride at the temperature of 60-80 ℃, reacting for 3-8h, removing the solvent, washing and drying to prepare the beta-cyclodextrin coated 1,1' -ferrocene diformyl chloride;
(3) in a nitrogen atmosphere, adding beta-cyclodextrin to coat 1,1' -ferrocene diformyl chloride into a dichloromethane solvent, adding 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide after uniformly dispersing by ultrasonic, stirring for reaction, carrying out reduced pressure distillation, washing and drying to prepare the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant;
(4) adding beta-cyclodextrin to the distilled aqueous solvent to coat the ferrocene-organophosphorus composite flame retardant, adding methyl methacrylate, acrylic acid and n-butyl acrylate after ultrasonic dispersion is uniform, dropwise adding an aqueous solution of ammonium ceric nitrate for reaction, filtering, washing and dialyzing to remove impurities, and preparing the ferrocene-organophosphorus reactive flame retardant modified acrylic resin.
2. The ferrocene-organophosphorus reactive flame retardant modified acrylic resin of claim 1, wherein: the mass ratio of the beta-cyclodextrin to the 1,1' -ferrocene diformyl chloride in the step (2) is 8-15: 10.
3. The ferrocene-organophosphorus reactive flame retardant modified acrylic resin of claim 1, wherein: the mass ratio of the beta-cyclodextrin coated 1,1' -ferrocene diformyl chloride to the 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in the step (3) is 100: 40-70.
4. The ferrocene-organophosphorus reactive flame retardant modified acrylic resin of claim 1, wherein: the reaction temperature in the step (3) is 20-30 ℃, and the reaction time is 12-24 h.
5. The ferrocene-organophosphorus reactive flame retardant modified acrylic resin of claim 1, wherein: the mass ratio of the beta-cyclodextrin coated ferrocene-organophosphorus composite flame retardant, the methyl methacrylate, the acrylic acid, the n-butyl acrylate and the ammonium ceric nitrate in the step (4) is 0.5-5:100:2-8: 5-15.
6. The ferrocene-organophosphorus reactive flame retardant modified acrylic resin of claim 1, wherein: the reaction temperature in the step (4) is 60-80 ℃, and the reaction time is 6-12 h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113388158A (en) * | 2020-03-12 | 2021-09-14 | 内蒙古浩普科技有限公司 | Application of phenylphosphono-hydrogen ferrocene as smoke suppressant in epoxy resin |
| CN113773553A (en) * | 2021-09-22 | 2021-12-10 | 东莞理工学院 | A kind of halogen-free flame retardant and preparation method thereof |
| CN113788903A (en) * | 2021-10-08 | 2021-12-14 | 福建工程学院 | Bio-based smoke suppressant and preparation method and application thereof |
| CN118813192A (en) * | 2024-09-19 | 2024-10-22 | 金华市奇昇新材料有限公司 | A composite water-based film heat-sealing adhesive and preparation method thereof |
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2020
- 2020-07-09 CN CN202010658915.7A patent/CN111675785A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113388158A (en) * | 2020-03-12 | 2021-09-14 | 内蒙古浩普科技有限公司 | Application of phenylphosphono-hydrogen ferrocene as smoke suppressant in epoxy resin |
| CN113388158B (en) * | 2020-03-12 | 2022-06-03 | 内蒙古浩普科技有限公司 | Application of phenylphosphono-hydrogen ferrocene as smoke suppressant in epoxy resin |
| CN113773553A (en) * | 2021-09-22 | 2021-12-10 | 东莞理工学院 | A kind of halogen-free flame retardant and preparation method thereof |
| CN113773553B (en) * | 2021-09-22 | 2022-12-13 | 东莞理工学院 | Halogen-free flame retardant and preparation method thereof |
| CN113788903A (en) * | 2021-10-08 | 2021-12-14 | 福建工程学院 | Bio-based smoke suppressant and preparation method and application thereof |
| CN118813192A (en) * | 2024-09-19 | 2024-10-22 | 金华市奇昇新材料有限公司 | A composite water-based film heat-sealing adhesive and preparation method thereof |
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