CN117024635A - Method for preparing pentabromobenzyl polyacrylate - Google Patents
Method for preparing pentabromobenzyl polyacrylate Download PDFInfo
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- CN117024635A CN117024635A CN202310936847.XA CN202310936847A CN117024635A CN 117024635 A CN117024635 A CN 117024635A CN 202310936847 A CN202310936847 A CN 202310936847A CN 117024635 A CN117024635 A CN 117024635A
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- pentabromobenzyl
- reaction
- aluminum
- preparing
- anhydrous isopropanol
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- 238000000034 method Methods 0.000 title claims abstract description 23
- -1 pentabromobenzyl Chemical group 0.000 title claims description 31
- 229920000058 polyacrylate Polymers 0.000 title claims description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000010992 reflux Methods 0.000 claims abstract description 24
- GRKDVZMVHOLESV-UHFFFAOYSA-N (2,3,4,5,6-pentabromophenyl)methyl prop-2-enoate Chemical compound BrC1=C(Br)C(Br)=C(COC(=O)C=C)C(Br)=C1Br GRKDVZMVHOLESV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005886 esterification reaction Methods 0.000 claims abstract description 17
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 13
- PYOIYKRKAHYOKO-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(bromomethyl)benzene Chemical compound BrCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br PYOIYKRKAHYOKO-UHFFFAOYSA-N 0.000 claims abstract description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- LIQDVINWFSWENU-UHFFFAOYSA-K aluminum;prop-2-enoate Chemical compound [Al+3].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C LIQDVINWFSWENU-UHFFFAOYSA-K 0.000 claims abstract description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 11
- 239000013557 residual solvent Substances 0.000 abstract description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052794 bromium Inorganic materials 0.000 abstract description 8
- 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 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229940048053 acrylate Drugs 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 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
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
- C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
-
- 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
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing pentabromobenzyl acrylate, which is characterized in that aluminum metal and anhydrous isopropanol enough to induce reaction start to react in a reflux state, the anhydrous isopropanol is supplemented to react to prepare aluminum isopropoxide, acrylic acid is directly added into reaction liquid to react to obtain aluminum acrylate, and esterification reaction is carried out on the aluminum acrylate and pentabromobenzyl bromide to prepare pentabromobenzyl acrylate monomer, and polymerization reaction is continued in the anhydrous isopropanol solution to obtain the target product of the pentabromobenzyl acrylate. The method prepares the target product with high bromine content and no residual solvent by monomer synthesis and polymerization reaction in an anhydrous environment, and is suitable for being applied to special industries with extremely high flame retardant requirements and other requirements.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a bromine-containing flame retardant poly (pentabromobenzyl acrylate), in particular to a preparation method of poly (pentabromobenzyl acrylate).
Background
The appearance of the pentabromobenzyl polyacrylate (FR-1025) is similar to white powder, and the monomer of the pentabromobenzyl polyacrylate contains five bromine atoms, and the bromine content is up to 71%, so that the pentabromobenzyl polyacrylate has relatively high market selling price, belongs to the category of high-end flame retardant products, and is a high-molecular weight environment-friendly bromine flame retardant with excellent performance.
The pentabromobenzyl polyacrylate has high flame retardant efficiency and good thermal stability, does not change the melting temperature, crystallization temperature and latent heat of materials and does not change the crystallinity of materials when being used for flame retarding PBT, has excellent processing fluidity and toughness compared with other brominated flame retardants used for PBT or polyamide nylon, has less addition amount and good compatibility with matrix resin, and is particularly suitable for thin walls, complex structures and other occasions requiring high fluidity, high toughness and high comprehensive performance.
In the actual production of the pentabromobenzyl polyacrylate, products with different molecular masses and different functional groups can be produced through process adjustment so as to adapt to the requirements of different industries.
The polyacrylate part in the pentabromobenzyl polyacrylate can effectively promote the compatibility of a polymer base material and a flame retardant, can greatly reduce or inhibit the occurrence of molten drops, has the advantages of no damage to the mechanical property of the material and difficult aging, and has the characteristics of migration resistance, no frosting, low toxicity and good thermal stability. In addition, pentabromobenzyl in pentabromobenzyl polyacrylate imparts excellent UV resistance to the flame retarded polymer, which is not comparable to many other brominated flame retardants. The pentabromobenzyl polyacrylate does not release cancerogenic substances such as dioxin and the like when being burnt, and has stronger competitive advantage which other flame retardants do not have.
Because of the excellent performance of the product, the product has wide application in industries with special requirements, such as textile fibers of military clothing, banknote ink and high-grade aerospace electronic products.
The existing synthetic route of the pentabromobenzyl acrylate is to carry out esterification reaction on pentabromobenzyl bromide and acrylic acid under the condition of water content to generate a pentabromobenzyl acrylate monomer, and then to generate a product by polymerization reaction.
Specifically, the first step of esterification reaction is to react acrylic acid with sodium hydroxide in water solution to generate sodium acrylate, then to perform esterification reaction in different solvents to generate pentabromobenzyl acrylate monomer, and then to polymerize the monomer in high boiling point and oily organic solvents by using a phase transfer catalyst and an initiator to form a product.
For example, CN 105523936a discloses a process for preparing pentabromobenzyl acrylate monomers and polymerization thereof, which comprises mixing pentabromobenzyl bromide, a phase transfer catalyst and a majority of aqueous alkali acrylate solution with a water-immiscible organic solvent, heating for reacting for a period of time, collecting an organic phase, adding the remaining aqueous alkali acrylate solution, continuing the heating for reacting, and separating to obtain pentabromobenzyl acrylate product.
The preparation process has the problems that the esterification reaction and the polymerization reaction are carried out in two phases of an aqueous phase and a water-insoluble organic phase, and although a special stirring mode and different phase transfer catalysts are adopted in the process, the aqueous phase and the organic phase are not always in good contact, so that the quality of the prepared product is easily unstable, and particularly the high-boiling point and oily residual solvent in the product is difficult to remove, so that the method cannot meet the application in some high-requirement industries.
The final polymerization reaction of the domestic production enterprises is carried out in a mixed solvent of water and chlorobenzene, and the final product is crystallized in the chlorobenzene. Chlorobenzene has a boiling point of 132 ℃ and a relatively high viscosity, so that chlorobenzene is more or less contained in the product crystals, and the chlorobenzene contained in the product crystals is inexhaustible no matter how dry, so that the residual solvent of the pentabromobenzyl polyacrylate product is disqualified. Taking military, paper money and space electronic products as examples, the residual solvent of the required products is zero, and the quality of self-produced products in China is unqualified, so that the current demands are almost all imported from israel.
Disclosure of Invention
The invention aims to provide a method for preparing pentabromobenzyl polyacrylate, which is used for preparing a target product with high bromine content and no residual solvent by reacting in an anhydrous environment.
The method for preparing the pentabromobenzyl acrylate comprises the steps of firstly reacting metal aluminum with anhydrous isopropanol which is enough to induce reaction in the presence of aluminum halide, continuously supplementing the anhydrous isopropanol, preparing aluminum isopropoxide by reaction in the reflux state, directly adding acrylic acid into reaction liquid to react to obtain aluminum acrylate, esterifying the aluminum acrylate with pentabromobenzyl bromide to prepare a pentabromobenzyl acrylate monomer, and continuously polymerizing the pentabromobenzyl acrylate monomer in the anhydrous isopropanol solution to obtain the target product of the pentabromobenzyl acrylate.
Wherein, the added anhydrous isopropanol enough to induce the reaction is preferably 7-10% of the total volume of the anhydrous isopropanol added in the process of preparing aluminum isopropoxide.
The practice of the invention proves that when the esterification reaction is carried out by aluminum acrylate in an anhydrous isopropanol solvent system, no side reaction is basically detected. If methanol is used as a solvent, side reactions are numerous in the esterification reaction with sodium methoxide, and it is impossible to carry out the reaction in production. Therefore, the pentabromobenzyl polyacrylate prepared by the method of the invention has higher bromine content, and no harmful high boiling point residual solvent is detected in the product.
Specifically, in the preparation method of aluminum isopropoxide, anhydrous isopropanol which is enough to induce the reaction is heated to 50 ℃ to react with aluminum metal slowly, the temperature is continuously raised to 82 ℃ to form reflux, the reflux reaction state is maintained to supplement the anhydrous isopropanol, and the reaction is continued to prepare the aluminum isopropoxide.
More specifically, in the invention, the aluminum isopropoxide reaction liquid is preferably obtained by reflux reaction for 2-4 hours after the anhydrous isopropanol is fully added.
Wherein, in the preparation of the aluminum isopropoxide, the mass ratio of the metal aluminum to the aluminum halide is preferably 1:0.05-0.1, and the mass of the anhydrous isopropanol enough to induce the reaction is 3-6 times of the mass of the metal aluminum.
Further, in the preparation method of the invention, when preparing the aluminum acrylate, the molar ratio of the added acrylic acid to the raw material metal aluminum is 2.95-3.1:1.
Furthermore, the preparation of the aluminum acrylate specifically comprises the step of reacting acrylic acid with aluminum isopropoxide reaction liquid at 50-82 ℃ for 1-2 h.
Further, in the preparation method of the invention, the molar ratio of the pentabromobenzyl bromide added in the esterification reaction to the raw material metal aluminum is 2.95-3.1:1.
Furthermore, the dosage of the solvent anhydrous isopropanol in the esterification reaction is preferably 3-5 times of the mass of the raw material pentabromobenzyl bromide.
In the preparation method of the invention, the esterification reaction is carried out under reflux at the temperature of 82 ℃ which is raised to the boiling point of isopropanol, and the preferred esterification reaction time is 4-8 h.
Further, in the preparation method of the invention, the initiator azodiisobutyronitrile added in the polymerization reaction is 1-3% of the mass of the raw material pentabromobenzyl bromide.
Further, the polymerization is also carried out under reflux at a boiling point temperature of 82℃of anhydrous isopropyl alcohol, and the polymerization time is preferably 1 to 4 hours.
In the preparation method, after the reaction is finished, the reaction solution is cooled to 5-15 ℃ and filtered, and a filter cake is washed with a little anhydrous isopropanol and dried, so that the target product of the pentabromobenzyl polyacrylate is prepared.
In the method for preparing the pentabromobenzyl acrylate, which is provided by the invention, the synthesis of the pentabromobenzyl acrylate monomer and the polymerization reaction of the monomer are carried out by adopting anhydrous isopropanol as a solvent under the anhydrous condition, and the product is dried after the polymerization reaction is finished, so that the content of residual solvent in the finally prepared product is zero.
The pentabromobenzyl polyacrylate prepared by the method has high quality, and is suitable for being applied to special industries with extremely high flame retardant requirements and other requirements.
Description of the embodiments
The following describes the present invention in further detail with reference to examples. The following examples are presented only to more clearly illustrate the technical aspects of the present invention so that those skilled in the art can better understand and utilize the present invention without limiting the scope of the present invention.
The production process, the experimental method or the detection method related to the embodiment of the invention are all conventional methods in the prior art unless otherwise specified, and the names and/or the abbreviations thereof are all conventional names in the field, so that the related application fields are very clear and definite, and a person skilled in the art can understand the conventional process steps according to the names and apply corresponding equipment to implement according to conventional conditions or conditions suggested by manufacturers.
The various instruments, equipment, materials or reagents used in the examples of the present invention are not particularly limited in source, and may be conventional products commercially available through regular commercial routes or may be prepared according to conventional methods well known to those skilled in the art.
Examples
Example 1
50mL of anhydrous isopropanol is added into a 1000mL three-necked flask, 1g of aluminum tribromide and 10g of aluminum sheet with the thickness of 3-5mm are added, the temperature is raised to 50 ℃, the reaction is slowly started, the temperature is gradually raised, and reflux is formed when the temperature is raised to 82 ℃, so that the reflux reaction state is maintained.
600mL of anhydrous isopropanol is added dropwise into a three-necked bottle at the speed of 60mL/h, and reflux reaction is continued for 2h after the completion of the dripping, so as to obtain an aluminum isopropoxide reaction liquid.
And cooling the aluminum isopropoxide reaction solution to 60 ℃, adding 80g of acrylic acid at one time, and maintaining the temperature of 60 ℃ for reaction for 2 hours to generate aluminum acrylate.
After the reaction, the reaction solution is filtered and pressed into a 3000mL esterification kettle by nitrogen, 2000mL of anhydrous isopropanol is added under stirring, 617g of dry pentabromobenzyl bromide is added, the temperature is raised to 82 ℃, and esterification reaction is carried out for 6 hours under reflux, so that pentabromobenzyl acrylate and aluminum bromide are generated.
After the reaction is finished, the temperature is reduced to 75 ℃, insoluble matters in the reaction liquid are removed by nitrogen pressure filtration, filtrate is collected in a polymerization kettle, 6.3g of azodiisobutyronitrile is added, the temperature is increased to 82 ℃ under stirring, and the polymerization is carried out for 2 hours under reflux.
After the reaction is finished, the reaction solution is cooled to 10 ℃ and filtered, and a filter cake is washed with a little anhydrous isopropanol and dried, so that the target product of the pentabromobenzyl polyacrylate is prepared.
The bromine content of the target product is 71.4 percent through detection, and the residual solvent isopropanol is not detected in the product.
Example 2
50L of anhydrous isopropanol is added into a 1000L stainless steel reaction kettle, 0.5Kg of aluminum tribromide and 10Kg of aluminum sheet with the thickness of 3mm are added, the temperature is raised to 50 ℃, the reaction is slowly started, the temperature is gradually raised, and reflux is formed when the temperature is raised to 82 ℃, so that the reflux reaction state is maintained.
And uniformly dripping 500L of anhydrous isopropanol into the reaction kettle at the speed of 1L/min until the dripping is finished, and continuing the reflux reaction for 4 hours to obtain an aluminum isopropoxide reaction liquid.
And cooling the aluminum isopropoxide reaction solution to 60 ℃, adding 80Kg of acrylic acid at one time, and maintaining the temperature of 60 ℃ for reaction for 1h to generate aluminum acrylate.
After the reaction, the reaction solution is filtered and pressed into a 3000L esterification kettle by nitrogen, 2100L anhydrous isopropanol and 615Kg pentabromobenzyl bromide are continuously added under stirring, the temperature is raised to 82 ℃, and esterification reaction is carried out for 8 hours under reflux, so that pentabromobenzyl acrylate and aluminum bromide are generated.
After the reaction is finished, the temperature is reduced to 70 ℃, insoluble matters in the reaction liquid are removed by nitrogen pressure filtration, the filtrate is collected in a polymerization kettle, 8Kg of azodiisobutyronitrile is added, the temperature is increased to 82 ℃ under stirring, and the polymerization is carried out for 3 hours under reflux.
After the reaction is finished, the reaction solution is cooled to 5 ℃ and filtered, and a filter cake is washed with a little anhydrous isopropanol and dried, so that the target product of the pentabromobenzyl polyacrylate is obtained.
The bromine content of the target product is 71.5 percent through detection, and the residual solvent isopropanol is not detected in the product.
The above embodiments of the invention are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Various changes, modifications, substitutions and alterations may be made by those skilled in the art without departing from the principles and spirit of the invention, and it is intended that the invention encompass all such changes, modifications and alterations as fall within the scope of the invention.
Claims (10)
1. The method for preparing the pentabromobenzyl acrylate comprises the steps of firstly reacting metal aluminum with anhydrous isopropanol which is enough to induce reaction in the presence of aluminum halide under a reflux state, continuously supplementing the anhydrous isopropanol, preparing aluminum isopropoxide by reaction under the reflux state, directly adding acrylic acid into a reaction liquid to react to obtain aluminum acrylate, esterifying the aluminum acrylate with pentabromobenzyl bromide to prepare a pentabromobenzyl acrylate monomer, and continuously polymerizing the pentabromobenzyl acrylate monomer in the anhydrous isopropanol solution to obtain the target product of the pentabromobenzyl acrylate.
2. The method for preparing pentabromobenzyl polyacrylate according to claim 1, characterized in that the anhydrous isopropanol sufficient to induce the reaction is 7-10% of the total anhydrous isopropanol volume added during the preparation of aluminum isopropoxide.
3. The method for preparing pentabromobenzyl polyacrylate according to claim 1, wherein the anhydrous isopropanol sufficient to induce the reaction is heated to 50 ℃ to react with aluminum metal slowly, the temperature is continuously raised to 82 ℃ to form reflux, the reflux reaction state is maintained to supplement the anhydrous isopropanol, and the reaction is continued to prepare aluminum isopropoxide.
4. The method for preparing pentabromobenzyl polyacrylate of claim 3, wherein the reflux reaction is carried out for 2-4 hours after the whole addition of anhydrous isopropanol.
5. The method for preparing pentabromobenzyl polyacrylate according to claim 1, characterized in that the mass ratio of metallic aluminum to aluminum halide is 1:0.05-0.1, and the mass of anhydrous isopropyl alcohol sufficient to induce the reaction is 3-6 times the mass of metallic aluminum.
6. The process for preparing pentabromobenzyl polyacrylate of claim 1, characterized in that the molar ratio of acrylic acid to aluminum metal is 2.95-3.1:1.
7. The method for preparing pentabromobenzyl polyacrylate according to claim 1, wherein the reaction between acrylic acid and aluminum isopropoxide is carried out at 50-82 ℃ for 1-2 h.
8. The method for preparing pentabromobenzyl polyacrylate according to claim 1, wherein the molar ratio of pentabromobenzyl bromide to aluminum metal added in the esterification reaction is 2.95-3.1:1, and the anhydrous isopropanol solvent is 3-5 times the mass of pentabromobenzyl bromide.
9. The method for preparing pentabromobenzyl polyacrylate according to claim 1, wherein the esterification reaction is carried out at 82 ℃ under reflux for 4-8 hours.
10. The method for preparing pentabromobenzyl polyacrylate according to claim 1, wherein the polymerization is carried out at 82 ℃ under reflux for 1-4 hours.
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