CN104177516B - A kind of brominated aliphatic alkene/vinyl aromatic copolymer fire retardant and preparation method thereof - Google Patents
A kind of brominated aliphatic alkene/vinyl aromatic copolymer fire retardant and preparation method thereof Download PDFInfo
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- CN104177516B CN104177516B CN201410460391.5A CN201410460391A CN104177516B CN 104177516 B CN104177516 B CN 104177516B CN 201410460391 A CN201410460391 A CN 201410460391A CN 104177516 B CN104177516 B CN 104177516B
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- vinyl aromatic
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 48
- 125000004067 aliphatic alkene group Chemical group 0.000 title claims abstract description 30
- 239000003063 flame retardant Substances 0.000 title abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000005893 bromination reaction Methods 0.000 claims abstract description 31
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 150000001336 alkenes Chemical class 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 37
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 28
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N Carbon tetrachloride Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 10
- -1 hexamethylene, Pentamethylene Chemical group 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- 229940001607 sodium bisulfite Drugs 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- JQRYUMGHOUYJFW-UHFFFAOYSA-N pyridine;trihydrobromide Chemical compound [Br-].[Br-].[Br-].C1=CC=[NH+]C=C1.C1=CC=[NH+]C=C1.C1=CC=[NH+]C=C1 JQRYUMGHOUYJFW-UHFFFAOYSA-N 0.000 claims description 3
- QARVLSVVCXYDNA-UHFFFAOYSA-N Bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 2
- JPOXNPPZZKNXOV-UHFFFAOYSA-N Bromochloromethane Chemical compound ClCBr JPOXNPPZZKNXOV-UHFFFAOYSA-N 0.000 claims description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N Cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 239000004914 cyclooctane Substances 0.000 claims description 2
- 150000004816 dichlorobenzenes Chemical class 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011968 lewis acid catalyst Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- KFUSEUYYWQURPO-UHFFFAOYSA-N 1,2-Dichloroethene Chemical compound ClC=CCl KFUSEUYYWQURPO-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- DEIGXXQKDWULML-MOCCIAMBSA-N (1R,2R,5R,6S,9S,10R)-1,2,5,6,9,10-hexabromocyclododecane Chemical compound Br[C@H]1CC[C@H](Br)[C@H](Br)CC[C@@H](Br)[C@H](Br)CC[C@H]1Br DEIGXXQKDWULML-MOCCIAMBSA-N 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 8
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-Dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(E)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 abstract 3
- VUQVJIUBUPPCDB-UHFFFAOYSA-N (1-bromo-2,2-diphenylethenyl)benzene Chemical compound C=1C=CC=CC=1C(Br)=C(C=1C=CC=CC=1)C1=CC=CC=C1 VUQVJIUBUPPCDB-UHFFFAOYSA-N 0.000 abstract 1
- SHKKTLSDGJRCTR-UHFFFAOYSA-N 1,2-dibromoethylbenzene Chemical compound BrCC(Br)C1=CC=CC=C1 SHKKTLSDGJRCTR-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- 239000005062 Polybutadiene Substances 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 229920002857 polybutadiene Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 229920001397 Poly-beta-hydroxybutyrate Polymers 0.000 description 4
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive Effects 0.000 description 4
- 125000001246 bromo group Chemical group Br* 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K Iron(III) chloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 125000004432 carbon atoms Chemical group C* 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004794 expanded polystyrene Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 229920000578 graft polymer Polymers 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 238000007347 radical substitution reaction Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-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
- SWLVFNYSXGMGBS-UHFFFAOYSA-N Ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachlorobutadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 description 1
- 229940030980 Inova Drugs 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 210000004940 Nucleus Anatomy 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000000240 adjuvant Effects 0.000 description 1
- 229940077484 ammonium bromide Drugs 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 230000003078 antioxidant Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005039 chemical industry Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000004059 degradation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002045 lasting Effects 0.000 description 1
- 230000004301 light adaptation Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Abstract
The invention provides a kind of brominated aliphatic alkene/vinyl aromatic copolymer fire retardant, alternatively HBCD is used for the general fire retardant of plastic industry；The bromination fat olefinic component of this brominated aliphatic alkene/vinyl aromatic copolymer fire retardant, including at least a kind of brominated olefins monomer, ethylene bromide base aromatic component include 2 bromstyrol bases, 4 bromstyrol bases, 2,4 Dowspray 9 bases, 6 bromstyrol bases, 2,4,6 phenylstilbene bromide bases.Also relate to the preparation method of this kind of brominated aliphatic alkene/vinyl aromatic copolymer fire retardant.
Description
Technical field
The present invention relates to chemical industry plastic additive field, particularly relate to a kind of thermal stable bromated aliphatic alkene/vinyl aromatic copolymer fire retardant, and the preparation method of this type of brominated aliphatic alkene/vinyl aromatic copolymer.
Background technology
HBCD (HBCD) is that a kind of general fire retardant (FR) has a wide range of applications in flame retardant area.But research finds, HBCD internal has bioaccumulation, to the toxicity of water plant and to there being lasting environmental effect at one or more.This is accomplished by certain laws and rules and limits and control for the use of HBCD, to reduce its impact for environmental and biological materials.Meanwhile, find a kind of in vivo without accumulation, the fire retardant of impact low on environment just seem extremely important.
Due to organism for polymer without absorbing polymer low migration in material simultaneously, aggretion type brominated flame-retardant is just that instead of a selection of HCBD.What is more important, aggretion type brominated flame-retardant inherently can be by adjusting the segment distribution of material, molecular weight distribution, the processing request of the different polymeric material of bromination rate adaptation.
The processing method that polymer is conventional has injection, extrusion, miscible and foamed polymer.For the processing method that these are different, the requirement for fire retardant is different.Wherein former three needs main heat stability the latter focusing on material may more focus on the compatibility of material.As a example by polystyrene, owing to polystyrene is in extrusion injection, melt mixed and extrusion and foaming process, its processing temperature is sometimes more than 200 DEG C, even up to 230 DEG C, require that its flame-retardant additive also should possess preferable heat stability, to prevent it from producing thermal degradation in the polystyrene course of processing.If flame-retardant additive decomposes during expressing technique or foam process, then it is faced with following Railway Project: fire retardant loses；The reduction of fire retardant performance；The generation of corrosivity catabolite, and the existence of these catabolites is potentially hazardous to environment and human body.Therefore flame-retardant additive is to focus on its heat stability at expressing technique or foam process temperature, and these processing temperatures are generally more than 200 DEG C, even up to 230 DEG C.But for the bromide fire retardant of expanded polystyrene (EPS), in addition to above-mentioned heat stability, they are the most more focused on to its compatibility in the material.Requirement emphasis for material is placed on itself and foaming post-consumer polymer, monomer before foaming, and the compatibility of foaming agent.On this basis, the fire resistance of fire retardant is improved as far as possible.For the bromide fire retardant of expanded polystyrene (EPS), it is considered that its bromine content is the highest, fire resistance is the best.Its fire resistance can be passed through limited oxygen index (LOI) and measure, and its value is the highest, illustrates that fire resistance is the best.Such as, after being added in expandable polystyrene by HBCD, bromine content LOI value of its foamed materials prepared when 0.6% is more than 25.
Many open source literatures report the synthesis of brominated polybutadiene homopolymer, but owing to there is no enough heat stability so that it is the succedaneum that cannot function as HBCD uses.Including:
French Patent (FRP) FR 1506872 describes the synthesis of polybutadiene bromination homopolymer, wherein polybutadiene preferred polymers be 5 to 200, most preferably 10 to 50 and its 1,2-group percentage is more than 50%.With carbon tetrachloride and butanol as mixed solvent, bromine is used to carry out bromination.
CN102174149 discloses the method preparing butadiene bromide copolymer.But the specific features of butadiene copolymer before its undeclared bromination.
WO2008/021417 describes the method for brominated butadiene polymers.Bromating agent is phenyl trialkyl tribromide ammonium, benzyl trialkyl tribromide ammonium or tetraalkyl tribromide ammonium.The method starting polymer is carried out in the solution.Realizing the high selective bromination of aliphatic series carbon-carbon double bond, aromatic ring is essentially unaffected.
CN102939308 discloses the method for brominated butadiene polymers.Bromating agent is tetraethyl list ammonium bromide.The method starting polymer is carried out in the solution.
In order to improve the heat stability of fire retardant, improving its application performance in materials processing, aromatic rings is incorporated in polybutadiene main chain by people.
JP 571113372 discloses the material of the expandable polystyrene of a kind of fire retardant (SBR) prepared containing bromination irregular phenylethylene-butadiene copolymer rubber.This SBR material is liquid, has relatively low molecular weight, and application performance is restricted.
CN 101305022 discloses the method preparing brominated butadiene/vinyl aromatic copolymer.Wherein preferred molecular weight is 50,000 to 100, and in the range of 000, with the mixture of oxolane or carbon tetrachloride and alcohol as solvent, using bromine or bromination is that the aliphatic double bonds in brominating agent polymer is to prepare brominated polymer.Its 5% thermal weight loss temperature is more than 200 DEG C.Bromination prepolymer medium vinyl aromatic monomer content is more than 5%.But aromatic rings is not carried out bromination by it.
Above two documents, it is achieved that the high selective bromination of fat carbon-carbon double bond, aromatic ring is essentially unaffected.But occurring in that a new problem, that is, due to the introducing of aromatic rings so that the bromine content of polymer reduces, the fire resistance of fire retardant declines simultaneously.
Summary of the invention
The technical problem to be solved provides a kind of brominated aliphatic alkene/vinyl aromatic copolymer fire retardant, and alternatively HBCD is used for the general fire retardant of plastic industry.Also relate to the preparation method of this kind of brominated aliphatic alkene/vinyl aromatic copolymer fire retardant.
The bromination fat olefinic component of this brominated aliphatic alkene/vinyl aromatic copolymer fire retardant, including at least a kind of brominated olefins monomer, ethylene bromide base aromatic component include 2-bromstyrol base, 4-bromstyrol base, 2,4-Dowspray 9 base, 6-bromstyrol base, 2,4,6-phenylstilbene bromide bases.
Further, described brominated aliphatic alkene/vinyl aromatic copolymer fire retardant, it is characterized in that: the fatty olefinic component of described aliphatic alkene/vinyl aromatic copolymer, including at least a kind of diene monomers or monoolefine monomer, diene monomers includes butadiene, isoprene, and monoolefine monomer includes methacrylic acid, acrylate.
Further, described brominated aliphatic alkene/vinyl aromatic copolymer fire retardant, it is characterized in that: the aromatic component of described aliphatic alkene/vinyl aromatic copolymer, at least one is selected from styrene, and this copolymer can be block copolymer, random copolymer or graft copolymer.
Further, described brominated aliphatic alkene/vinyl aromatic copolymer fire retardant, it is characterised in that: the weight average molecular weight of described aliphatic alkene/vinyl aromatic copolymer is between 1000 to 60000, and preferable weight-average molecular weight is between 5000-10000.
A kind of method preparing brominated aliphatic alkene/vinyl aromatic copolymer involved in the present invention, described method includes:
Step 1) adds aliphatic alcohol after being uniformly dissolved with stirring solvent by aliphatic alkene/vinyl aromatic copolymer and mixs homogeneously, bromating agent is dripped in this solution, and making mixture reaction until the aliphatic diene unit of required ratio is brominated, bromination reaction measures the aliphatic double bonds content of bromination in the copolymer after bromination by 1H-NMR；
Step 2) it is subsequently added lewis acid catalyst continuation reaction a period of time, until the aromatic rings unit of required ratio is brominated in aliphatic alkene/vinyl aromatic copolymer, bromination reaction measures in the copolymer after bromination bromine content on the aromatic rings of bromination by 1H-NMR；
Step 3) is after reaction obtains the polymer of required bromine content, by washing, precipitate or program is recovered by filtration, from reaction solution, remove by-product, then filtrate is removed, by silica gel or ion exchange resin bed, the by-product remained, polymer is deposited in methanol recovery brominated polymer.
Aliphatic alkene/vinyl aromatic copolymer in described step 1), wherein comprising vinyl aromatic composition by weight percent is 5 to 90% and aliphatic alkene composition by weight percent is the weight average molecular weight of 10 to 95%, at least 800；
Further, the fatty olefinic component of described aliphatic alkene/vinyl aromatic copolymer, including at least a kind of diene monomers or monoolefine monomer, diene monomers includes butadiene, isoprene, monoolefine monomer includes that methacrylic acid, acrylate, aliphatic alkene/vinyl aromatic copolymer can be block copolymer, random copolymer or graft copolymer.
In described step 1), bromating agent is the mixture that bromating agent comprises bromine and free radical scavenger.
Further, under substantially not having free radical substitution reaction, bromination ion, with cation state and aliphatic chain alkene generation bromination reaction, is preferably carried out under entirely without free radical substitution reaction；In fat alkene bromination process, add free radical scavenger or use the method for preferred bromating agent or solvent to prepare brominated polymer, it has of a sufficiently low tertiary bromine content, can avoid generating heat-labile polymer, using 5% thermal weight loss temperature as the indirect indexes of tertiary bromine content, show when 5% thermal weight loss temperature is more than 200 DEG C, having of a sufficiently low tertiary bromine content, preferably 5% thermal weight loss temperature is more than 205 DEG C, more preferably greater than 210 DEG C, even more preferably greater than 220 DEG C.
Further, described bromating agent comprises bromine and tribromide, and tribromide includes pyridinium tribromide, tribromide phenyltrimethyammonium, tetra-alkylammonium tribromide.
Solvent in described step 1), under atmospheric pressure, solvent has the boiling point less than 100 DEG C (especially less than 80 DEG C), is substantially immiscible, is sprotic in water, and without the hydrogen atom being attached on tertiary carbon atom or oxygen；Solvent is easier to volatilization than water, easily removes from water.Ethers such as oxolane can be selected；Halogenated alkane such as carbon tetrachloride, chloroform, dichloromethane, bromochloromethane and 1,2-dichloroethanes；Hydro carbons such as hexamethylene, Pentamethylene., cyclooctane and toluene, and halogenated aromatic compound such as bromobenzene, chlorobenzene and dichloro-benzenes；
Further, halogenated alkane, the cycloalkane not containing the hydrogen atom being attached on tertiary carbon atom and halogenated aromatic compound are preferred solvents.Two kinds of especially preferred solvents are dichloroethanes and hexamethylene.
Described step 1) selects the amount of aliphatic alcohol so that every mole elemental bromine relative in bromating agent, it is provided that at least 0.5 mole of aliphatic alcohol, and starting fat race alkene/vinyl aromatic copolymer remains dissolved in reactant mixture.Some aliphatic alcohols play inverse solvent (antisolvents) for starting copolymer and act on, and therefore being present in excess of they may make starting copolymer precipitate from solution.The amount of aliphatic alcohol is 0.5-6 moles/mole elemental bromine, and preferably amount is 0.75-3.5 moles/mole elemental bromine, and optimal preferably amount is 1.00-1.05 moles/mole elemental bromine.Can use more than the amount of this tittle, premise is that starting copolymer keeps solubilized.Generally, it is seldom necessary to use more than 1 moles of alcohol per mole elemental bromine.
Described step 2) in lewis acid comprise metallic antimony, titanium, ferrum or stannum and halogenide thereof.
Recycling step in described step 3), it be also possible to use aqueous solution of sodium bisulfite and fully washs from the filtrate of ion exchange resin bed outflow with the unreacted bromating agent neutralized or cancellation there may be filtrate.
Described in described step 3), the blend of brominated copolymer includes flame-retardant additive, flame retardant adjuvants, heat stabilizer, UV light stabilizing agent, nucleator, antioxidant, foaming agent, plumper and coloring agent.
From the invention described above content, compared to the prior art, present invention have the advantage that
The present invention carries out bromination reaction to aliphatic double bonds and aromatic rings respectively, it is on the basis of aliphatic chain high selectivity bromination, further bromination aromatic rings, improves the bromination rate of polymer, and then the fire resistance of raising material, there is extraordinary heat stability and fire resistance.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
To join equipped with in the 250ml there-necked flask of mechanical agitator and constant pressure funnel in 6.6g (polystyrene-b-butadiene) copolymer (polybutadiene unit of 0.075 mole of polymerized) and 70 ml carbon tetrachloride solutions, stirring and dissolving adds 25ml n-butanol mix homogeneously the most afterwards.At room temperature dripping the bromine of 12.6 g (0.08 mole) in solution, in 20 min, dropping is complete.Reactant mixture is shown as heat release in bromine adding procedure, and the maximum temperature of course of reaction is 45 DEG C.After continuing reaction under reactant mixture room temperature 15 hours, 0.01g adds ferric chloride, continues reaction 2h, then adds the 20wt% aqueous solution of sodium bisulfite of 50 ml.Then proceed to stir 15 minutes, add the dichloromethane of 60ml afterwards.Reactant mixture is transferred to separatory funnel, and upper strata is aqueous phase, and lower floor is organic facies.
Organic facies 50ml distilled water is washed, washs with 50ml saturated nacl aqueous solution subsequently.Organic facies after washing joins in the methanol of 5 times of excess (based on liquor capacity), is precipitated by brominated polymer from the organic facies after washing.By the polymer filtration of precipitation and at 80 DEG C, dried in vacuum overnight, obtain the brominated polymer of 16.9g (88% separates productivity).The 1H-NMR of brominated polymer shows 2.3% unreacted double bond, and 4.5% virtue ring hydrogen is replaced by bromine, and TGA analyzes 5% weightless temperature of display 225 DEG C.
Embodiment 2
To join equipped with in the 250ml there-necked flask of mechanical agitator and constant pressure funnel in poly-for 6.6g (styrene-b-butadiene) copolymer (polybutadiene unit of 0.075 mole of polymerized) and 70 ml dichloromethane solutions, stirring and dissolving adds 25ml n-butanol mix homogeneously the most afterwards.After dissolution of the polymer, solution is cooled in ice bath 1 DEG C, the bromine of 12.6 g (0.008 mole) is dripped in solution, in 20 min, dropping is complete, in holding reaction bulb, temperature is at or below 7 DEG C, after continuing stirring 20 minutes, add 0.01g and add ferric chloride, continue reaction 30min, remove ice bath, and by reaction solution solution with 20% aqueous solution of sodium bisulfite (51g), then with water (50g), then with saturated sodium-chloride water solution (59g) wash, after extract with dichloromethane.Organic facies after washing joins in the methanol of 5 times of excess (based on liquor capacity), brominated polymer is precipitated from the organic facies after washing, by the polymer filtration of precipitation and at 80 DEG C, dried in vacuum overnight, obtain the brominated polymer of 16.5g (86% separates productivity).The 1H-NMR of brominated polymer shows 1.8% unreacted double bond, and 4.5 % virtue ring hydrogens are replaced by bromine, and TGA analyzes 5% weightless temperature of display 223 DEG C.
Embodiment 3
To join equipped with in the 250ml there-necked flask of mechanical agitator and constant pressure funnel in poly-for 6.6g (styrene-b-butadiene) copolymer (polybutadiene unit of 0.075 mole of polymerized) and 70 ml dichloromethane solutions, stirring and dissolving adds 25ml n-butanol mix homogeneously the most afterwards.After dissolution of the polymer, solution is cooled in ice bath 1 DEG C.Dripping 20 ml THF solution containing 25.6 g pyridinium tribromide (0.008 mole) in solution, in 30 min, dropping is complete.In holding reaction bulb, temperature is at or below 7 DEG C, after continuing stirring 20 minutes, adds 0.01g and adds ferric chloride, continuation reaction 30min, remove ice bath；And reaction solution is removed by-product hydrogen pyridinium bromide (PHB) by filtering, by resulting polymers solution by cation exchange resin bed to remove the PHB of residual from solution, then with 20% aqueous solution of sodium bisulfite (51g), then with water (50g), then with saturated sodium-chloride water solution (59g) wash, after extract with dichloromethane.Organic facies after washing joins in the methanol of 5 times of excess (based on liquor capacity), brominated polymer is precipitated from the organic facies after washing, by the polymer filtration of precipitation and at 80 DEG C, dried in vacuum overnight, obtain the brominated polymer of 16.5g (86% separates productivity), the 1H-NMR of brominated polymer shows 1.3% unreacted double bond, 4.8 % virtue ring hydrogens are replaced by bromine, and TGA analyzes 5% weightless temperature of display 228 DEG C, by-product hydrogen pyridinium bromide (PHB) is removed by filtering, by resulting polymers solution by cation exchange resin bed to remove the PHB of residual from solution.
Thermal performance analysis and fire resistance analysis
Thermal weight loss temperature test
The TGA 400 that use Perkinelmer company produces is in the range of 50 to 600 DEG C under the rate of heat addition of 10 DEG C/min, and under nitrogen atmosphere, (flow velocity is 20mL/min) carries out testing (sample quality is 8-12 mg).This method provide 5% thermal weight loss temperature of sample, and initial weightless temperature.
Molecular weight is tested
Molecular weight test is carried out on HP 1090 HPLC type chromatograph of gel permeation, detached dowel model 5 mm Phenogel columns (linear 300*4.6 mm, 5 micro), column temperature 36 DEG C, flowing is oxolane mutually, and butadiene is reference material, Composition distribution.
Nucleus n-ness spectrum is tested
Nuclear magnetic resonance, NMR test is carried out on Varian Unity Inova 400, and with deuterium band chloroform as solvent, TMS is internal standard, and test temperature is 25 DEG C.
Oxygen index (OI) is tested
LOI test is carried out according to GB/T 2406.2.For solid sample, prepare the sample of 100mm × 6.5mm × 1.5mm.For foam sample, improve being directed to use with foam line mould and produce to there is the foam rods of 5mm girth and rod is cut into 150mm length and test.
Following bromo polybutadiene styrene polymer is prepared respectively according to embodiment 3.And heat stability and the fire resistance of material is measured according to the test program of standard, its measurement result and fire resistance are as follows:
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, should be included within the scope of the present invention.
Claims (5)
1. the method preparing brominated aliphatic alkene/vinyl aromatic copolymer, described method includes:
Step 1) aliphatic alkene/vinyl aromatic copolymer is uniformly dissolved with stirring solvent after add aliphatic alcohol mix homogeneously,
Solution is cooled in ice bath 1 DEG C, and in dripping bromating agent, 20-30min in solution, dropping is complete, and makes mixture anti-
Should be until the aliphatic diene unit of required ratio be brominated, bromination reaction is measured in the copolymer after bromination by 1H-NMR
The aliphatic double bonds content of bromination；The consumption of described aliphatic alcohol so that every mole elemental bromine relative in bromating agent, it is provided that at least
0.5 mole of aliphatic alcohol, and starting fat race alkene/vinyl aromatic copolymer remains dissolved in reactant mixture；
Step 2) keep temperature in reaction bulb at or below 7 DEG C, after continuing to stir 20 minutes, to add lewis acid catalyst,
Continue reaction 30min, until the aromatic rings unit of required ratio is brominated in aliphatic alkene/vinyl aromatic copolymer, bromine
Change reaction and measure in the copolymer after bromination bromine content on the aromatic rings of bromination by 1H-NMR；
Step 3) after reaction obtains the polymer of required bromine content, by washing, precipitate or program is recovered by filtration, molten from reaction
Liquid is removed by-product, then filtrate is removed, by silica gel or ion exchange resin bed, the by-product remained, polymer is deposited in
Methanol reclaims brominated polymer.
A kind of method preparing brominated aliphatic alkene/vinyl aromatic copolymer, its feature exists
In described step 1) in solvent be oxolane, carbon tetrachloride, chloroform, dichloromethane, bromochloromethane, 1,2-bis-chloroethene
One in alkane, hexamethylene, Pentamethylene., cyclooctane, toluene, bromobenzene, chlorobenzene or dichloro-benzenes.
A kind of method preparing brominated aliphatic alkene/vinyl aromatic copolymer, its feature exists
In: described bromating agent comprises bromine and tribromide, tribromide include pyridinium tribromide, tribromide phenyltrimethyammonium,
Tetra-alkylammonium tribromide.
A kind of method preparing brominated aliphatic alkene/vinyl aromatic copolymer, its feature exists
In described step 2) in the catalyst of bromination reaction of aromatic rings be lewis acid, lewis acid comprises metallic antimony, titanium, ferrum
Or stannum and halogenide thereof.
A kind of method preparing brominated aliphatic alkene/vinyl aromatic copolymer, its feature exists
In described step 3) in it be also possible to use aqueous solution of sodium bisulfite fully wash the filtrate flowed out from ion exchange resin bed with
With or the cancellation unreacted bromating agent in filtrate.
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| CN201410460391.5A CN104177516B (en) | 2014-09-11 | A kind of brominated aliphatic alkene/vinyl aromatic copolymer fire retardant and preparation method thereof |
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| CN201410460391.5A CN104177516B (en) | 2014-09-11 | A kind of brominated aliphatic alkene/vinyl aromatic copolymer fire retardant and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101213220A (en) * | 2005-06-30 | 2008-07-02 | 雅宝公司 | Brominated styrenic polymers and their preparation |
| CN103649211A (en) * | 2011-07-14 | 2014-03-19 | 陶氏环球技术有限责任公司 | Impact-modified styrenic polymers containing brominated vinyl aromatic-butadiene copolymer |
| CN103649191A (en) * | 2011-07-14 | 2014-03-19 | 陶氏环球技术有限责任公司 | Selective gas transport films that contain brominated styrene-butadiene copolymers |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101213220A (en) * | 2005-06-30 | 2008-07-02 | 雅宝公司 | Brominated styrenic polymers and their preparation |
| CN103649211A (en) * | 2011-07-14 | 2014-03-19 | 陶氏环球技术有限责任公司 | Impact-modified styrenic polymers containing brominated vinyl aromatic-butadiene copolymer |
| CN103649191A (en) * | 2011-07-14 | 2014-03-19 | 陶氏环球技术有限责任公司 | Selective gas transport films that contain brominated styrene-butadiene copolymers |
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