CN117362522A - Preparation method of brominated styrene/butadiene copolymer - Google Patents
Preparation method of brominated styrene/butadiene copolymer Download PDFInfo
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- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 42
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 119
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 239000007800 oxidant agent Substances 0.000 claims abstract description 33
- 230000001590 oxidative effect Effects 0.000 claims abstract description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001816 cooling Methods 0.000 claims abstract description 31
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 29
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- UZIQYAYUUNMDMU-UHFFFAOYSA-N N.[Br+] Chemical compound N.[Br+] UZIQYAYUUNMDMU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 70
- 238000002156 mixing Methods 0.000 claims description 46
- 230000008569 process Effects 0.000 claims description 46
- 239000002131 composite material Substances 0.000 claims description 43
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 40
- 239000007787 solid Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 27
- 239000012153 distilled water Substances 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 20
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 19
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 229910052797 bismuth Inorganic materials 0.000 claims description 18
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 18
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 238000003825 pressing Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 16
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 229920001447 polyvinyl benzene Polymers 0.000 claims description 16
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 15
- 239000012286 potassium permanganate Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 12
- 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 claims description 10
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims description 10
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 claims description 4
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 239000011159 matrix material Substances 0.000 abstract description 8
- 229920001577 copolymer Polymers 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000003063 flame retardant Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 16
- 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 description 12
- 239000007795 chemical reaction product Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 7
- 238000007885 magnetic separation Methods 0.000 description 7
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 238000000643 oven drying Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 230000031709 bromination Effects 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-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
- NTHFKMZKTASAMH-UHFFFAOYSA-N 2,4-dibromo-1-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C(Br)=C1 NTHFKMZKTASAMH-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007269 dehydrobromination reaction Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 230000004580 weight loss Effects 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a brominated styrene/butadiene copolymer, which comprises the steps of firstly, taking styrene and butadiene as raw materials to carry out polymerization reaction to obtain the styrene/butadiene copolymer; then uniformly dispersing the styrene/butadiene copolymer in the isobutanol, then adding an organic bromine ammonium salt aqueous solution, slowly and uniformly adding an oxidant while stirring, and heating and stirring after the oxidant is fed; cooling, adding magnetic catalyst, heating, applying pulse magnetic field, stirring under heat-insulating condition, and post-treating. The copolymer obtained by the invention has excellent flame retardance and thermal stability, and can improve the toughness of products after being added to a resin matrix.
Description
Technical Field
The invention relates to a preparation method of a flame retardant, in particular to a preparation method of a brominated styrene/butadiene copolymer. Belonging to the technical field of synthesis of brominated flame retardants.
Background
The brominated flame retardant is one of the most widely applied flame retardants at present, has the advantages of good flame retardance and high efficiency, good thermal stability and the like, can meet the flame retardance requirements of various high polymer materials, and has sufficient raw material sources and low price. Brominated flame retardants can be broadly classified into small molecule flame retardants and high molecule flame retardants according to the molecular weight. Polybrominated diphenyl ethers are very common commercial small-molecule flame retardants, have the disadvantages of having a molecular weight of less than 500, being easy to separate out from a polymer material matrix, and generating carcinogens such as dioxin during combustion, thereby severely polluting the environment. The hexabromocyclododecane product is also a commonly used additive flame retardant on the market, is mainly used as polystyrene, polypropylene, ABS, polycarbonate, unsaturated polyester and the like, and recent researches show that the hexabromocyclododecane has extremely strong bioaccumulative toxicity in organisms, is harmful to aquatic organisms or environment, has high toxicity, and has become severe in dehydrobromination of the hexabromocyclododecane at the temperature of more than 190 ℃. The hazard of hydrogen bromide vapor is more pronounced and toxic and hazardous fumes are produced when used as a flame retardant.
In order to solve the environmental protection problem, attempts are made to develop halogen-free flame retardants, however, halogen-free flame retardants have the problems of low flame retardant efficiency, high addition amount, high price, high cost and the like, are basically used in products such as toys, clothes and the like which are in close contact with human bodies, and have poor market acceptance for building material products and the like.
Compared with halogen-free flame retardant, the low-toxicity high-molecular brominated flame retardant has better feasibility by improving the molecular weight and the molecular structure. Compared with a small molecular flame retardant, the high molecular flame retardant has obviously better flame retardant effect, has a long-chain structure, is not easy to migrate and has better environmental protection. Brominated styrene PBS, brominated polystyrene BPS, brominated epoxy resin BEP, brominated polycarbonate BCO and the like belong to high molecular flame retardants. Among them, PBS has high bromine content and good flame retardance, but the rigid aromatic chain segment reduces the toughness of the material when the PBS is compounded with a substrate.
Patent application CN104327214a discloses a brominated styrene/butadiene copolymer flame retardant and a bromination method thereof, the copolymer is polymerized by brominated styrene monomer and butadiene monomer components, and in the brominated styrene/butadiene copolymer, brominated aryl groups of styrene comprise 2-bromostyrene, 4-bromostyrene and 2, 4-dibromostyrene.
Patent CN101305022B discloses a heat stable brominated copolymer, such as a brominated styrene/butadiene block copolymer, a brominated random styrene/butadiene copolymer or a brominated styrene/butadiene graft copolymer, the preparation of a brominated butadiene copolymer, the use of a brominated butadiene copolymer as a flame retardant additive, and foamed and non-foamed polymer compositions incorporating a flame retardant amount of a brominated butadiene copolymer.
The two patent technologies have advantages and disadvantages, and the obtained product has room for improvement in terms of flame retardance, thermal stability, influence on toughness of a resin matrix and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a preparation method of a brominated styrene/butadiene copolymer, which has excellent flame retardance and thermal stability and can improve the toughness of a product after being added to a resin matrix.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the brominated styrene/butadiene copolymer comprises the following specific steps in parts by weight:
(1) Firstly, polymerizing styrene and butadiene serving as raw materials to obtain a styrene/butadiene copolymer;
(2) Then uniformly dispersing 1 part of styrene/butadiene copolymer in 8-10 parts of isobutanol, then adding 3-5 parts of organic bromine ammonium salt aqueous solution with the mass concentration of 35-45%, slowly and uniformly adding 0.1-0.2 part of oxidant under the condition of 25-30 ℃, and heating and stirring after the oxidant is fed;
(3) Cooling, adding 0.01-0.015 part of magnetic catalyst, heating, applying a pulse magnetic field, preserving heat, stirring, and post-treating to obtain the catalyst;
wherein the oxidant is a compound of ammonium phosphomolybdate and bismuth vanadate-manganese dioxide according to the mass ratio of 1:0.2 to 0.3; the magnetic catalyst is prepared by the following steps: firstly, mixing the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material with nano alumina and gamma-ferric oxide, pressing the mixture into a sheet material, and then mixing the sheet material with 1-ethyl-3-methylimidazole chloroaluminate to obtain the composite material.
Preferably, the specific method of the step (1) is as follows: under the protection of nitrogen, adding styrene and tetrahydrofuran into normal hexane, stirring and heating to 50-55 ℃, continuously adding normal butyl lithium, keeping the temperature and stirring for 30-40 minutes, adding butadiene, reacting for 120-180 minutes under the conditions of 50-55 ℃ and 0.1-0.2 MPa, adding distilled water to terminate the reaction, and performing post-treatment to obtain the catalyst; wherein, the mass ratio of the styrene, the butadiene, the n-butyllithium, the tetrahydrofuran, the n-hexane and the distilled water is 3:6.5 to 7.5:0.07 to 0.08:1.2 to 1.5: 15-17: 0.001 to 0.002.
Further preferably, the specific method of post-treatment is as follows: adding the reaction product into distilled water with the weight 5-6 times of that of the reaction product, evaporating at 100 ℃ to remove the solvent, separating and suspending the polymer in a solid state, filtering and separating to obtain a solid, and drying.
Preferably, in the step (2), the organic ammonium bromide salt is selected from any one of tetrabutylammonium bromide, benzyltrimethylammonium bromide and dodecyldimethylbenzyl ammonium bromide.
Preferably, in step (2), the oxidant is fed for 30 to 40 minutes.
Preferably, in the step (2), the process conditions of heating and stirring are as follows: stirring and heating to 55-65 ℃, and preserving heat and stirring for 50-70 minutes.
Preferably, in the step (3), the temperature is reduced to 20-25 ℃.
Preferably, in the step (3), stirring and heating are carried out to 70-80 ℃, and the heat preservation and stirring time is 30-40 minutes.
Preferably, in the step (3), the process conditions of the pulsed magnetic field are: the magnetic field intensity is 10-15T, the pulse width is 8-10 ms, and the pulse interval is 15-20 s.
Preferably, in step (3), the post-treatment includes: naturally cooling to room temperature, filtering to obtain solid, magnetically separating to recover magnetic catalyst, washing the residue with water for 2-3 times, and stoving at 70-80 deg.c for 10-12 hr.
Preferably, the bismuth vanadate-manganese dioxide compound is prepared by the following method in parts by weight: dissolving 2-3 parts of bismuth nitrate pentahydrate in 20-25 parts of 2-3 mol/L dilute nitric acid to obtain bismuth nitrate solution, adding ammonium metavanadate, stirring and mixing uniformly, dropwise adding 2-3 mol/L sodium hydroxide solution until pH=6-6.5, adding potassium permanganate, stirring and mixing uniformly, reacting at 190-200 ℃ for 20-24 hours, naturally cooling, filtering to obtain solid, washing with distilled water for 2-3 times, and drying to obtain the bismuth nitrate; wherein, the ammonium metavanadate and the potassium permanganate are in equimolar quantity with bismuth nitrate pentahydrate.
Further preferably, the drying process conditions are as follows: and drying at 70-80 ℃ for 10-12 hours.
Preferably, in preparing the magnetic catalyst, the process conditions of the mixing process are as follows: under the condition of 0.1-0.2 MPa, ultrasonic oscillation is carried out for 30-40 minutes at 25-35 kHz and 300-400W, and solid is extracted by suction filtration; the mass ratio of the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material to the nano aluminum oxide to the gamma-ferric oxide to the 1-ethyl-3-methylimidazole chloroaluminate is 1:1 to 1.5:0.1 to 0.2:3 to 4.
Preferably, when preparing the magnetic catalyst, polyvinyl alcohol is also added as a forming agent, the dosage of the forming agent is 0.5 to 0.7 percent of the mass of the polydivinylbenzene-polyvinylbenzene sulfonic acid composite material, and the pressing process conditions are as follows: 300-350 MPa to be pressed into a sheet with the thickness of 1-2 mm.
Preferably, the polydivinylbenzene-polyvinylbenzene sulfonic acid composite material is prepared by the following method: firstly, divinylbenzene and azodiisobutyronitrile are added into tetrahydrofuran, sodium p-styrenesulfonate is added into the mixture for stirring for the first time, the mixture is stirred for the second time, the mixture reacts for 20 to 24 hours at the temperature of 80 to 90 ℃ and the pressure of 0.1 to 0.2MPa, the mixture is naturally cooled to the temperature of the mixture, and the solvent is volatilized at the room temperature to remove the mixture to obtain the catalyst; wherein the mass ratio of divinylbenzene, azodiisobutyronitrile, sodium p-styrenesulfonate and tetrahydrofuran is 4-5: 1:0.4 to 0.5:35 to 45.
Further preferably, the process conditions of the first stirring are: stirring for 30-40 minutes at 300-400 r/min; the process conditions of the second stirring are as follows: stirring for 2-3 hours at 300-400 r/min.
The invention has the beneficial effects that:
the method comprises the steps of firstly, polymerizing styrene and butadiene serving as raw materials to obtain a styrene/butadiene copolymer; then uniformly dispersing the styrene/butadiene copolymer in the isobutanol, then adding an organic bromine ammonium salt aqueous solution, slowly and uniformly adding an oxidant while stirring, and heating and stirring after the oxidant is fed; cooling, adding a magnetic catalyst, heating, applying a pulse magnetic field, preserving heat, stirring, and performing aftertreatment to obtain the brominated styrene/butadiene copolymer. The copolymer obtained by the invention has excellent flame retardance and thermal stability, and can improve the toughness of products after being added to a resin matrix.
The initial raw material styrene/butadiene copolymer of the invention is prepared by self, the number average molecular weight range is 15000-20000, the molecular weight distribution is 1.0-1.1, and the product is ensured to have certain toughness.
The invention uses organic bromine ammonium salt to realize bromination, the bromination process is easier to control, and the bromination efficiency is ensured, so that the product has good flame retardance, does not damage the main structure, and maintains the toughness and the thermal stability of the product.
The catalyst used in the invention has magnetism, a pulse magnetic field is applied in the reaction process, and the catalyst is fully brominated through the coupling effect of the magnetic field and heating, so that the product is endowed with excellent flame retardance, thermal stability and toughness.
The oxidant adopts the combination of ammonium phosphomolybdate and bismuth vanadate-manganese dioxide compound, and the two parts of the compounds are synergistic to promote the copolymerization reaction, wherein the bismuth vanadate-manganese dioxide compound is prepared by the following method: dissolving bismuth nitrate pentahydrate in dilute nitric acid to obtain bismuth nitrate solution, adding ammonium metavanadate, stirring and mixing uniformly, adjusting pH to be 6-6.5, adding potassium permanganate, stirring and mixing uniformly, heating and reacting, and carrying out post-treatment to obtain the bismuth nitrate pentahydrate. The synergistic selective oxidation of ammonium phosphomolybdate and bismuth vanadate-manganese dioxide compound does not destroy the main chain structure, improves the flame retardance of the product, and does not influence the toughness and the thermal stability of the product.
The magnetic catalyst is prepared by the following steps: firstly, mixing the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material with nano alumina and gamma-ferric oxide, pressing the mixture into a sheet material, and then mixing the sheet material with 1-ethyl-3-methylimidazole chloroaluminate to obtain the composite material. The gamma-ferric oxide not only provides magnetism, but also plays a role in catalysis in cooperation with the polydivinylbenzene-polyethylene benzenesulfonic acid composite material and the nano aluminum oxide, and the magnetic catalyst plays a role similar to a solid acid catalyst, reduces side reactions and promotes reaction, so that the product has excellent flame retardance, thermal stability and toughness. After the reaction is finished, the magnetic catalyst can be recovered through magnetic separation, and the method is simple and quick.
Detailed Description
The present invention will be further illustrated by the following examples, which are given by way of illustration only and are not intended to be limiting.
1-ethyl-3-methylimidazole chloroaluminate, available from Jiahui Hubei Hui Xincheng Biotechnology Co., ltd;
gamma-ferric oxide, available from Andi metal materials Co., ltd.
Example 1:
a preparation method of a brominated styrene/butadiene copolymer comprises the following specific steps:
(1) Under the protection of nitrogen, adding 3kg of styrene and 1.2kg of tetrahydrofuran into 15kg of n-hexane, stirring and heating to 50 ℃, continuously adding 0.07kg of n-butyllithium, keeping the temperature and stirring for 30 minutes, adding 6.5kg of butadiene, reacting for 120 minutes at 50 ℃ and 0.1MPa, adding 0.001kg of distilled water to terminate the reaction, adding the reaction product into distilled water which is 5 times of the reaction product, evaporating at 100 ℃ to remove the solvent, separating and suspending the polymer in a solid state, filtering and separating to obtain a solid, and drying to obtain the styrene/butadiene copolymer;
(2) Then 1kg of styrene/butadiene copolymer is evenly dispersed in 8kg of isobutanol, then 3kg of organic bromine ammonium salt water solution with the mass concentration of 35% is added, 0.1kg of oxidant is slowly and uniformly added under the condition of 25 ℃ while stirring (30 minutes are taken for feeding), and after the oxidant is fed, the mixture is stirred and heated to 55 ℃, and the mixture is kept at the temperature and stirred for 50 minutes;
(3) Cooling to 20deg.C, adding 0.01kg of magnetic catalyst, stirring and heating to 70deg.C, applying pulse magnetic field, maintaining the temperature and stirring for 30 min, post-treating, naturally cooling to room temperature, filtering to obtain solid, recovering magnetic catalyst by magnetic separation, washing residue with water for 2 times, and oven drying at 70deg.C for 10 hr to obtain the final product;
wherein the oxidant is a compound of ammonium phosphomolybdate and bismuth vanadate-manganese dioxide according to the mass ratio of 1:0.2 mixing; the magnetic catalyst is prepared by the following steps: firstly, mixing the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material with nano alumina and gamma-ferric oxide, pressing the mixture into a sheet material, and then mixing the sheet material with 1-ethyl-3-methylimidazole chloroaluminate to obtain the composite material.
In the step (2), the organic ammonium bromide salt is tetrabutylammonium bromide.
In the step (3), the process conditions of the pulsed magnetic field are as follows: the magnetic field strength is 10T, the pulse width is 8ms, and the pulse interval is 15s.
The bismuth vanadate-manganese dioxide compound is prepared by the following method: dissolving 0.2kg of bismuth nitrate pentahydrate in 2kg of 2mol/L dilute nitric acid to obtain bismuth nitrate solution, adding ammonium metavanadate, stirring and mixing uniformly, dropwise adding 2mol/L sodium hydroxide solution until pH=6, adding potassium permanganate, stirring and mixing uniformly, reacting at 190 ℃ for 20 hours, naturally cooling, filtering to obtain solid, washing with distilled water for 2 times, and drying at 70 ℃ for 10 hours to obtain the bismuth nitrate; wherein, the ammonium metavanadate and the potassium permanganate are in equimolar quantity with bismuth nitrate pentahydrate.
When preparing the magnetic catalyst, the process conditions of the mixing processing are as follows: under the condition of 0.1MPa, carrying out ultrasonic oscillation for 30 minutes at 25kHz and 300W, and carrying out suction filtration to obtain a solid; the mass ratio of the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material to the nano aluminum oxide to the gamma-ferric oxide to the 1-ethyl-3-methylimidazole chloroaluminate is 1:1:0.1:3.
when the magnetic catalyst is prepared, polyvinyl alcohol is also added as a forming agent, the dosage of the forming agent is 0.5 percent of the mass of the polydivinylbenzene-polyvinylbenzene sulfonic acid composite material, and the pressing process conditions are as follows: 300MPa is pressed into a sheet with the thickness of 1 mm.
The polydivinylbenzene-polyvinylbenzene sulfonic acid composite material is prepared by the following method: adding 0.4kg of divinylbenzene and 0.1kg of azodiisobutyronitrile into 3.5kg of tetrahydrofuran, stirring for the first time, adding 0.04kg of sodium p-styrenesulfonate, stirring for the second time, reacting for 20 hours at 80 ℃ and 0.1MPa, naturally cooling to temperature, volatilizing at room temperature, and removing the solvent.
The process conditions of the first stirring are as follows: stirring for 30 minutes at 300 r/min; the process conditions of the second stirring are as follows: stirring for 2 hours at 300 r/min.
Example 2:
a preparation method of a brominated styrene/butadiene copolymer comprises the following specific steps:
(1) Under the protection of nitrogen, adding 3kg of styrene and 1.5kg of tetrahydrofuran into 17kg of n-hexane, stirring and heating to 55 ℃, continuously adding 0.08kg of n-butyllithium, keeping the temperature and stirring for 40 minutes, adding 7.5kg of butadiene, reacting for 180 minutes under the conditions of 55 ℃ and 0.2MPa, adding 0.002kg of distilled water to terminate the reaction, adding the reaction product into distilled water with the weight being 6 times that of the reaction product, evaporating at 100 ℃ to remove the solvent, separating and suspending the polymer in a solid state, filtering and separating the polymer to obtain solid, and drying to obtain the styrene/butadiene copolymer;
(2) Then 1kg of styrene/butadiene copolymer is evenly dispersed in 10kg of isobutanol, then 5kg of 45% organic bromine ammonium salt aqueous solution with mass concentration is added, 0.2kg of oxidant is slowly and uniformly added while stirring at 30 ℃ (40 minutes are taken for feeding), after the oxidant is fed, stirring and heating are carried out to 65 ℃, and the temperature is kept for 70 minutes;
(3) Cooling to 25deg.C, adding 0.015kg of magnetic catalyst, stirring and heating to 80deg.C, applying pulse magnetic field, maintaining the temperature and stirring for 40 min, post-treating, naturally cooling to room temperature, filtering to obtain solid, recovering magnetic catalyst by magnetic separation, washing residue with water for 3 times, and oven drying at 80deg.C for 12 hr to obtain the final product;
wherein the oxidant is a compound of ammonium phosphomolybdate and bismuth vanadate-manganese dioxide according to the mass ratio of 1:0.3 mixing; the magnetic catalyst is prepared by the following steps: firstly, mixing the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material with nano alumina and gamma-ferric oxide, pressing the mixture into a sheet material, and then mixing the sheet material with 1-ethyl-3-methylimidazole chloroaluminate to obtain the composite material.
In the step (2), the organic ammonium bromide salt is benzyl trimethyl ammonium bromide.
In the step (3), the process conditions of the pulsed magnetic field are as follows: the magnetic field strength is 15T, the pulse width is 10ms, and the pulse interval is 20s.
The bismuth vanadate-manganese dioxide compound is prepared by the following method: dissolving 0.3kg of bismuth nitrate pentahydrate in 2.5kg of 3mol/L dilute nitric acid to obtain bismuth nitrate solution, adding ammonium metavanadate, stirring and mixing uniformly, dropwise adding 3mol/L sodium hydroxide solution until the pH value is less than 6.5, adding potassium permanganate, stirring and mixing uniformly, reacting at 200 ℃ for 24 hours, naturally cooling, filtering to obtain a solid, washing with distilled water for 3 times, and drying at 80 ℃ for 12 hours to obtain the bismuth nitrate pentahydrate; wherein, the ammonium metavanadate and the potassium permanganate are in equimolar quantity with bismuth nitrate pentahydrate.
When preparing the magnetic catalyst, the process conditions of the mixing processing are as follows: under the condition of 0.2MPa, carrying out ultrasonic oscillation for 40 minutes at 35kHz and 400W, and carrying out suction filtration to obtain solid; the mass ratio of the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material to the nano aluminum oxide to the gamma-ferric oxide to the 1-ethyl-3-methylimidazole chloroaluminate is 1:1.5:0.2:4.
when the magnetic catalyst is prepared, polyvinyl alcohol is also added as a forming agent, the dosage of the forming agent is 0.7 percent of the mass of the polydivinylbenzene-polyvinylbenzene sulfonic acid composite material, and the pressing process conditions are as follows: pressing under 350MPa to obtain sheet with thickness of 2 mm.
The polydivinylbenzene-polyvinylbenzene sulfonic acid composite material is prepared by the following method: adding 0.5kg of divinylbenzene and 0.1kg of azodiisobutyronitrile into 4.5kg of tetrahydrofuran, stirring for the first time, adding 0.05kg of sodium p-styrenesulfonate, stirring for the second time, reacting for 24 hours at 90 ℃ and 0.2MPa, naturally cooling to temperature, volatilizing at room temperature, and removing the solvent.
The process conditions of the first stirring are as follows: stirring for 40 minutes at 400 r/min; the process conditions of the second stirring are as follows: stirring at 400r/min for 3 hours.
Example 3:
a preparation method of a brominated styrene/butadiene copolymer comprises the following specific steps:
(1) Under the protection of nitrogen, adding 3kg of styrene and 1.2kg of tetrahydrofuran into 17kg of n-hexane, stirring and heating to 50 ℃, continuously adding 0.08kg of n-butyllithium, keeping the temperature and stirring for 30 minutes, adding 7.5kg of butadiene, reacting for 120 minutes at 50 ℃ and 0.2MPa, adding 0.002kg of distilled water to terminate the reaction, adding the reaction product into distilled water which is 5 times of the reaction product, evaporating at 100 ℃ to remove the solvent, separating and suspending the polymer in a solid state, filtering and separating to obtain a solid, and drying to obtain the styrene/butadiene copolymer;
(2) Then 1kg of styrene/butadiene copolymer is evenly dispersed in 10kg of isobutanol, then 3kg of 45% organic bromine ammonium salt aqueous solution with mass concentration is added, 0.2kg of oxidant is slowly and uniformly added under the condition of 25 ℃ while stirring (30 minutes are taken for feeding), and after the oxidant is fed, stirring and heating are carried out to 65 ℃, and the temperature is kept for 50 minutes;
(3) Cooling to 25deg.C, adding 0.01kg of magnetic catalyst, stirring and heating to 80deg.C, applying pulse magnetic field, maintaining the temperature and stirring for 30 min, post-treating, naturally cooling to room temperature, filtering to obtain solid, recovering magnetic catalyst by magnetic separation, washing residue with water for 3 times, and oven drying at 70deg.C for 12 hr to obtain the final product;
wherein the oxidant is a compound of ammonium phosphomolybdate and bismuth vanadate-manganese dioxide according to the mass ratio of 1:0.2 mixing; the magnetic catalyst is prepared by the following steps: firstly, mixing the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material with nano alumina and gamma-ferric oxide, pressing the mixture into a sheet material, and then mixing the sheet material with 1-ethyl-3-methylimidazole chloroaluminate to obtain the composite material.
In the step (2), the organic bromine ammonium salt is dodecyl dimethyl benzyl ammonium bromide.
In the step (3), the process conditions of the pulsed magnetic field are as follows: the magnetic field strength is 15T, the pulse width is 8ms, and the pulse interval is 20s.
The bismuth vanadate-manganese dioxide compound is prepared by the following method: dissolving 0.2kg of bismuth nitrate pentahydrate in 2.5kg of 2mol/L dilute nitric acid to obtain bismuth nitrate solution, adding ammonium metavanadate, stirring and mixing uniformly, dropwise adding 3mol/L sodium hydroxide solution until the pH value is less than 6, adding potassium permanganate, stirring and mixing uniformly, reacting at 200 ℃ for 20 hours, naturally cooling, filtering to obtain solid, washing with distilled water for 3 times, and drying at 70 ℃ for 12 hours to obtain the bismuth nitrate pentahydrate; wherein, the ammonium metavanadate and the potassium permanganate are in equimolar quantity with bismuth nitrate pentahydrate.
When preparing the magnetic catalyst, the process conditions of the mixing processing are as follows: under the condition of 0.1MPa, carrying out ultrasonic oscillation for 40 minutes at 35kHz and 300W, and carrying out suction filtration to obtain solid; the mass ratio of the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material to the nano aluminum oxide to the gamma-ferric oxide to the 1-ethyl-3-methylimidazole chloroaluminate is 1:1:0.2:3.
when the magnetic catalyst is prepared, polyvinyl alcohol is also added as a forming agent, the dosage of the forming agent is 0.7 percent of the mass of the polydivinylbenzene-polyvinylbenzene sulfonic acid composite material, and the pressing process conditions are as follows: 300MPa is pressed into a sheet with the thickness of 2 mm.
The polydivinylbenzene-polyvinylbenzene sulfonic acid composite material is prepared by the following method: adding 0.4kg of divinylbenzene and 0.1kg of azodiisobutyronitrile into 4.5kg of tetrahydrofuran, stirring for the first time, adding 0.04kg of sodium p-styrenesulfonate, stirring for the second time, reacting for 24 hours at 90 ℃ and 0.1MPa, naturally cooling to temperature, volatilizing at room temperature, and removing the solvent.
The process conditions of the first stirring are as follows: stirring for 40 minutes at 300 r/min; the process conditions of the second stirring are as follows: stirring for 3 hours at 300 r/min.
Example 4:
a preparation method of a brominated styrene/butadiene copolymer comprises the following specific steps:
(1) Under the protection of nitrogen, adding 3kg of styrene and 1.3kg of tetrahydrofuran into 16kg of n-hexane, stirring and heating to 52 ℃, continuously adding 0.07kg of n-butyllithium, keeping the temperature and stirring for 35 minutes, adding 7kg of butadiene, reacting for 150 minutes at 52 ℃ and 0.2MPa, adding 0.001kg of distilled water to terminate the reaction, adding the product obtained by the reaction into distilled water which is 5.5 times of the weight of the product, evaporating at 100 ℃ to remove the solvent, separating and suspending the polymer in a solid state, filtering and separating the solid, and drying to obtain the styrene/butadiene copolymer;
(2) Then 1kg of styrene/butadiene copolymer is evenly dispersed in 9kg of isobutanol, then 4kg of 40% organic bromine ammonium salt aqueous solution with mass concentration is added, 0.15kg of oxidant is slowly and uniformly added under the condition of 27 ℃ while stirring (35 minutes are taken for feeding), and after the oxidant is fed, stirring and heating are carried out to 60 ℃, and the temperature is kept for 60 minutes;
(3) Cooling to 22deg.C, adding 0.012kg of magnetic catalyst, stirring and heating to 75deg.C, applying pulse magnetic field, maintaining the temperature and stirring for 35 min, post-treating, naturally cooling to room temperature, filtering to obtain solid, recovering magnetic catalyst by magnetic separation, washing residue with water for 3 times, and oven drying at 75deg.C for 11 hr to obtain the final product;
wherein the oxidant is a compound of ammonium phosphomolybdate and bismuth vanadate-manganese dioxide according to the mass ratio of 1: 0.25; the magnetic catalyst is prepared by the following steps: firstly, mixing the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material with nano alumina and gamma-ferric oxide, pressing the mixture into a sheet material, and then mixing the sheet material with 1-ethyl-3-methylimidazole chloroaluminate to obtain the composite material.
In the step (2), the organic ammonium bromide salt is benzyl trimethyl ammonium bromide.
In the step (3), the process conditions of the pulsed magnetic field are as follows: the magnetic field strength is 12T, the pulse width is 9ms, and the pulse interval is 18s.
The bismuth vanadate-manganese dioxide compound is prepared by the following method: dissolving 0.25kg of bismuth nitrate pentahydrate in 2.2kg of 2.5mol/L dilute nitric acid to obtain bismuth nitrate solution, adding ammonium metavanadate, stirring and mixing uniformly, dropwise adding 2.5mol/L sodium hydroxide solution until pH=6.5, adding potassium permanganate, stirring and mixing uniformly, reacting at 195 ℃ for 22 hours, naturally cooling, filtering to obtain solid, washing with distilled water for 3 times, and drying at 75 ℃ for 11 hours to obtain the bismuth nitrate pentahydrate; wherein, the ammonium metavanadate and the potassium permanganate are in equimolar quantity with bismuth nitrate pentahydrate.
When preparing the magnetic catalyst, the process conditions of the mixing processing are as follows: under the condition of 0.15MPa, 30kHz and 400W ultrasonic oscillation are carried out for 35 minutes, and the solid is extracted by suction filtration; the mass ratio of the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material to the nano aluminum oxide to the gamma-ferric oxide to the 1-ethyl-3-methylimidazole chloroaluminate is 1:1.2:0.15:3.5.
when the magnetic catalyst is prepared, polyvinyl alcohol is also added as a forming agent, the dosage of the forming agent is 0.6 percent of the mass of the polydivinylbenzene-polyvinylbenzene sulfonic acid composite material, and the pressing process conditions are as follows: 320MPa is pressed into a sheet with the thickness of 1.5 mm.
The polydivinylbenzene-polyvinylbenzene sulfonic acid composite material is prepared by the following method: adding 0.45kg of divinylbenzene and 0.1kg of azodiisobutyronitrile into 4kg of tetrahydrofuran, stirring for the first time, adding 0.045kg of sodium p-styrenesulfonate, stirring for the second time, reacting for 22 hours at the temperature of 85 ℃ and the pressure of 0.15MPa, naturally cooling to the temperature, and volatilizing at room temperature to remove the solvent to obtain the catalyst.
The process conditions of the first stirring are as follows: stirring for 35 minutes at 350 r/min; the process conditions of the second stirring are as follows: stirring at 350r/min for 2.5 hours.
Comparative example 1
A preparation method of a brominated styrene/butadiene copolymer comprises the following specific steps:
(1) Under the protection of nitrogen, adding 3kg of styrene and 1.2kg of tetrahydrofuran into 15kg of n-hexane, stirring and heating to 50 ℃, continuously adding 0.07kg of n-butyllithium, keeping the temperature and stirring for 30 minutes, adding 6.5kg of butadiene, reacting for 120 minutes at 50 ℃ and 0.1MPa, adding 0.001kg of distilled water to terminate the reaction, adding the reaction product into distilled water which is 5 times of the reaction product, evaporating at 100 ℃ to remove the solvent, separating and suspending the polymer in a solid state, filtering and separating to obtain a solid, and drying to obtain the styrene/butadiene copolymer;
(2) Then 1kg of styrene/butadiene copolymer is evenly dispersed in 8kg of isobutanol, then 3kg of organic bromine ammonium salt water solution with the mass concentration of 35% is added, 0.1kg of oxidant is slowly and uniformly added under the condition of 25 ℃ while stirring (30 minutes are taken for feeding), and after the oxidant is fed, the mixture is stirred and heated to 55 ℃, and the mixture is kept at the temperature and stirred for 50 minutes;
(3) Cooling to 20deg.C, adding 0.01kg of magnetic catalyst, stirring and heating to 70deg.C, applying pulse magnetic field, maintaining the temperature and stirring for 30 min, post-treating, naturally cooling to room temperature, filtering to obtain solid, recovering magnetic catalyst by magnetic separation, washing residue with water for 2 times, and oven drying at 70deg.C for 10 hr to obtain the final product;
wherein the oxidant is ammonium phosphomolybdate; the magnetic catalyst is prepared by the following steps: firstly, mixing the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material with nano alumina and gamma-ferric oxide, pressing the mixture into a sheet material, and then mixing the sheet material with 1-ethyl-3-methylimidazole chloroaluminate to obtain the composite material.
In the step (2), the organic ammonium bromide salt is tetrabutylammonium bromide.
In the step (3), the process conditions of the pulsed magnetic field are as follows: the magnetic field strength is 10T, the pulse width is 8ms, and the pulse interval is 15s.
When preparing the magnetic catalyst, the process conditions of the mixing processing are as follows: under the condition of 0.1MPa, carrying out ultrasonic oscillation for 30 minutes at 25kHz and 300W, and carrying out suction filtration to obtain a solid; the mass ratio of the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material to the nano aluminum oxide to the gamma-ferric oxide to the 1-ethyl-3-methylimidazole chloroaluminate is 1:1:0.1:3.
when the magnetic catalyst is prepared, polyvinyl alcohol is also added as a forming agent, the dosage of the forming agent is 0.5 percent of the mass of the polydivinylbenzene-polyvinylbenzene sulfonic acid composite material, and the pressing process conditions are as follows: 300MPa is pressed into a sheet with the thickness of 1 mm.
The polydivinylbenzene-polyvinylbenzene sulfonic acid composite material is prepared by the following method: adding 0.4kg of divinylbenzene and 0.1kg of azodiisobutyronitrile into 3.5kg of tetrahydrofuran, stirring for the first time, adding 0.04kg of sodium p-styrenesulfonate, stirring for the second time, reacting for 20 hours at 80 ℃ and 0.1MPa, naturally cooling to temperature, volatilizing at room temperature, and removing the solvent.
The process conditions of the first stirring are as follows: stirring for 30 minutes at 300 r/min; the process conditions of the second stirring are as follows: stirring for 2 hours at 300 r/min.
Comparative example 2
A preparation method of a brominated styrene/butadiene copolymer comprises the following specific steps:
(1) Under the protection of nitrogen, adding 3kg of styrene and 1.2kg of tetrahydrofuran into 15kg of n-hexane, stirring and heating to 50 ℃, continuously adding 0.07kg of n-butyllithium, keeping the temperature and stirring for 30 minutes, adding 6.5kg of butadiene, reacting for 120 minutes at 50 ℃ and 0.1MPa, adding 0.001kg of distilled water to terminate the reaction, adding the reaction product into distilled water which is 5 times of the reaction product, evaporating at 100 ℃ to remove the solvent, separating and suspending the polymer in a solid state, filtering and separating to obtain a solid, and drying to obtain the styrene/butadiene copolymer;
(2) Then 1kg of styrene/butadiene copolymer is evenly dispersed in 8kg of isobutanol, then 3kg of organic bromine ammonium salt water solution with the mass concentration of 35% is added, 0.1kg of oxidant is slowly and uniformly added under the condition of 25 ℃ while stirring (30 minutes are taken for feeding), and after the oxidant is fed, the mixture is stirred and heated to 55 ℃, and the mixture is kept at the temperature and stirred for 50 minutes;
(3) Cooling to 20deg.C, adding 0.01kg of magnetic catalyst, stirring and heating to 70deg.C, applying pulse magnetic field, maintaining the temperature and stirring for 30 min, post-treating, naturally cooling to room temperature, filtering to obtain solid, recovering magnetic catalyst by magnetic separation, washing residue with water for 2 times, and oven drying at 70deg.C for 10 hr to obtain the final product;
wherein the oxidant is a compound of ammonium phosphomolybdate and bismuth vanadate-manganese dioxide according to the mass ratio of 1:0.2 mixing; the magnetic catalyst is prepared by the following steps: firstly, mixing and pressing the polydivinylbenzene-polyvinylbenzene sulfonic acid composite material with nano alumina and gamma-ferric oxide to prepare a sheet material.
In the step (2), the organic ammonium bromide salt is tetrabutylammonium bromide.
In the step (3), the process conditions of the pulsed magnetic field are as follows: the magnetic field strength is 10T, the pulse width is 8ms, and the pulse interval is 15s.
The bismuth vanadate-manganese dioxide compound is prepared by the following method: dissolving 0.2kg of bismuth nitrate pentahydrate in 2kg of 2mol/L dilute nitric acid to obtain bismuth nitrate solution, adding ammonium metavanadate, stirring and mixing uniformly, dropwise adding 2mol/L sodium hydroxide solution until pH=6, adding potassium permanganate, stirring and mixing uniformly, reacting at 190 ℃ for 20 hours, naturally cooling, filtering to obtain solid, washing with distilled water for 2 times, and drying at 70 ℃ for 10 hours to obtain the bismuth nitrate; wherein, the ammonium metavanadate and the potassium permanganate are in equimolar quantity with bismuth nitrate pentahydrate.
When preparing the magnetic catalyst, the process conditions of the mixing processing are as follows: under the condition of 0.1MPa, carrying out ultrasonic oscillation for 30 minutes at 25kHz and 300W, and carrying out suction filtration to obtain a solid; the mass ratio of the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material to the nano aluminum oxide to the gamma-ferric oxide to the 1-ethyl-3-methylimidazole chloroaluminate is 1:1:0.1:3.
when the magnetic catalyst is prepared, polyvinyl alcohol is also added as a forming agent, the dosage of the forming agent is 0.5 percent of the mass of the polydivinylbenzene-polyvinylbenzene sulfonic acid composite material, and the pressing process conditions are as follows: 300MPa is pressed into a sheet with the thickness of 1 mm.
The polydivinylbenzene-polyvinylbenzene sulfonic acid composite material is prepared by the following method: adding 0.4kg of divinylbenzene and 0.1kg of azodiisobutyronitrile into 3.5kg of tetrahydrofuran, stirring for the first time, adding 0.04kg of sodium p-styrenesulfonate, stirring for the second time, reacting for 20 hours at 80 ℃ and 0.1MPa, naturally cooling to temperature, volatilizing at room temperature, and removing the solvent.
The process conditions of the first stirring are as follows: stirring for 30 minutes at 300 r/min; the process conditions of the second stirring are as follows: stirring for 2 hours at 300 r/min.
Performance test:
1. thermal stability
The brominated styrene/butadiene copolymers obtained in examples 1 to 4 and comparative examples 1 and 2 were subjected to thermal stability test using a thermogravimetric analyzer, 10mg of the brominated styrene/butadiene copolymer was taken under a nitrogen atmosphere of 60mL/min, and heated at a rate of 10℃per minute to determine a weight loss temperature of 5%.
2. Investigation of flame retardance and toughness
The brominated styrene/butadiene copolymers obtained in examples 1 to 4 and comparative examples 1 and 2 were compounded with a resin matrix (polystyrene) to obtain a resin material, respectively, and the lowest addition amount (percentage by mass of the total mass after mixing with the resin matrix) reaching V-0 was detected with reference to the UL94 standard.
The resin material obtained by compounding the lowest addition amount is used for testing the unnotched impact strength of the resin material by referring to GB/T1843-2008 'determination of impact strength of Plastic cantilever beam'.
The results of the performance test are shown in Table 1.
TABLE 1 Performance test results
As is clear from Table 1, the brominated styrene/butadiene copolymers obtained in examples 1 to 4 have good thermal stability, can achieve V-0 flame retardance with a lower addition amount by compounding with a resin matrix, and have higher toughness.
The oxidant in comparative example 1 omits bismuth vanadate-manganese dioxide compound, and the catalyst in comparative example 2 omits 1-ethyl-3-methylimidazole chloroaluminate, so that the thermal stability, flame retardance and toughness are obviously deteriorated, which shows that the oxidant and the catalyst form synergistic effect, so that the product has good flame retardance, and the thermal stability and toughness are improved.
While the foregoing describes the embodiments of the present invention, it is not intended to limit the scope of the present invention, and various modifications or variations may be made by those skilled in the art without the need for inventive effort on the basis of the technical solutions of the present invention.
Claims (9)
1. The preparation method of the brominated styrene/butadiene copolymer is characterized by comprising the following specific steps in parts by weight:
(1) Firstly, polymerizing styrene and butadiene serving as raw materials to obtain a styrene/butadiene copolymer;
(2) Then uniformly dispersing 1 part of styrene/butadiene copolymer in 8-10 parts of isobutanol, then adding 3-5 parts of organic bromine ammonium salt aqueous solution with the mass concentration of 35-45%, slowly and uniformly adding 0.1-0.2 part of oxidant under the condition of 25-30 ℃, and heating and stirring after the oxidant is fed;
(3) Cooling, adding 0.01-0.015 part of magnetic catalyst, heating, applying a pulse magnetic field, preserving heat, stirring, and post-treating to obtain the catalyst;
wherein the oxidant is a compound of ammonium phosphomolybdate and bismuth vanadate-manganese dioxide according to the mass ratio of 1:0.2 to 0.3; the magnetic catalyst is prepared by the following steps: firstly, mixing the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material with nano alumina and gamma-ferric oxide, pressing the mixture into a sheet material, and then mixing the sheet material with 1-ethyl-3-methylimidazole chloroaluminate to obtain the composite material.
2. The preparation method according to claim 1, wherein the specific method of step (1) is as follows: under the protection of nitrogen, adding styrene and tetrahydrofuran into normal hexane, stirring and heating to 50-55 ℃, continuously adding normal butyl lithium, keeping the temperature and stirring for 30-40 minutes, adding butadiene, reacting for 120-180 minutes under the conditions of 50-55 ℃ and 0.1-0.2 MPa, adding distilled water to terminate the reaction, and performing post-treatment to obtain the catalyst; wherein, the mass ratio of the styrene, the butadiene, the n-butyllithium, the tetrahydrofuran, the n-hexane and the distilled water is 3:6.5 to 7.5:0.07 to 0.08:1.2 to 1.5: 15-17: 0.001 to 0.002.
3. The process according to claim 1, wherein in step (2), the organic bromine ammonium salt is selected from any one of tetrabutylammonium bromide, benzyltrimethylammonium bromide, and dodecyldimethylbenzyl ammonium bromide;
the oxidant is fed for 30 to 40 minutes;
the process conditions of heating and stirring are as follows: stirring and heating to 55-65 ℃, and preserving heat and stirring for 50-70 minutes.
4. The method according to claim 1, wherein in the step (3), the temperature is reduced to 20-25 ℃;
stirring and heating to 70-80 ℃, and preserving heat and stirring for 30-40 minutes;
the process conditions of the pulsed magnetic field are as follows: the magnetic field intensity is 10-15T, the pulse width is 8-10 ms, and the pulse interval is 15-20 s;
the post-processing includes: naturally cooling to room temperature, filtering to obtain solid, magnetically separating to recover magnetic catalyst, washing the residue with water for 2-3 times, and stoving at 70-80 deg.c for 10-12 hr.
5. The preparation method of claim 1, wherein the bismuth vanadate-manganese dioxide composite is prepared by the following steps of: dissolving 2-3 parts of bismuth nitrate pentahydrate in 20-25 parts of 2-3 mol/L dilute nitric acid to obtain bismuth nitrate solution, adding ammonium metavanadate, stirring and mixing uniformly, dropwise adding 2-3 mol/L sodium hydroxide solution until pH=6-6.5, adding potassium permanganate, stirring and mixing uniformly, reacting at 190-200 ℃ for 20-24 hours, naturally cooling, filtering to obtain solid, washing with distilled water for 2-3 times, and drying to obtain the bismuth nitrate; wherein, the ammonium metavanadate and the potassium permanganate are in equimolar quantity with bismuth nitrate pentahydrate.
6. The method according to claim 1, wherein the process conditions for the mixing process in the preparation of the magnetic catalyst are: under the condition of 0.1-0.2 MPa, ultrasonic oscillation is carried out for 30-40 minutes at 25-35 kHz and 300-400W, and solid is extracted by suction filtration; the mass ratio of the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material to the nano aluminum oxide to the gamma-ferric oxide to the 1-ethyl-3-methylimidazole chloroaluminate is 1:1 to 1.5:0.1 to 0.2:3 to 4.
7. The preparation method according to claim 1, wherein in the preparation of the magnetic catalyst, polyvinyl alcohol is also added as a forming agent, the amount of the forming agent is 0.5-0.7% of the mass of the polydivinylbenzene-polyvinylbenzene sulfonic acid composite material, and the pressing process conditions are as follows: 300-350 MPa to be pressed into a sheet with the thickness of 1-2 mm.
8. The preparation method of claim 1, wherein the polydivinylbenzene-polyvinylbenzenesulfonic acid composite material is prepared by the following method: firstly, divinylbenzene and azodiisobutyronitrile are added into tetrahydrofuran, sodium p-styrenesulfonate is added into the mixture for stirring for the first time, the mixture is stirred for the second time, the mixture reacts for 20 to 24 hours at the temperature of 80 to 90 ℃ and the pressure of 0.1 to 0.2MPa, the mixture is naturally cooled to the temperature of the mixture, and the solvent is volatilized at the room temperature to remove the mixture to obtain the catalyst; wherein the mass ratio of divinylbenzene, azodiisobutyronitrile, sodium p-styrenesulfonate and tetrahydrofuran is 4-5: 1:0.4 to 0.5:35 to 45.
9. The method according to claim 8, wherein the first stirring process conditions are: stirring for 30-40 minutes at 300-400 r/min; the process conditions of the second stirring are as follows: stirring for 2-3 hours at 300-400 r/min.
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