CN102174149B - Method for producing butadiene bromide copolymer - Google Patents
Method for producing butadiene bromide copolymer Download PDFInfo
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- CN102174149B CN102174149B CN 201110049108 CN201110049108A CN102174149B CN 102174149 B CN102174149 B CN 102174149B CN 201110049108 CN201110049108 CN 201110049108 CN 201110049108 A CN201110049108 A CN 201110049108A CN 102174149 B CN102174149 B CN 102174149B
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229920001577 copolymer Polymers 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 38
- 239000012074 organic phase Substances 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000004821 distillation Methods 0.000 claims abstract description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000000967 suction filtration Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 235000002639 sodium chloride Nutrition 0.000 claims description 24
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 abstract 2
- 239000012267 brine Substances 0.000 abstract 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000003063 flame retardant Substances 0.000 description 14
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920006351 engineering plastic Polymers 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 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 2
- 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 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for producing butadiene bromide copolymer, comprising the following steps of: firstly, adding dichloroethane to a reaction kettle, then adding butadiene copolymer while stirring, and stirring for 25-35 minutes at room temperature; dripping n-butyl alcohol into the reaction kettle and stirring evenly; dripping bromine into the reaction kettle at 20-41 DEG C, heating to 40-42 DEG C, insulating and reacting for 13-17 hours; washing the material with alkali after reaction, stirring for 8-12 minutes, standing and layering; stirring the lower organic phase after alkali wash, standing and layering, then washing with water; stirring the lower organic phase after water wash, standing and layering; washing with brine, standing and layering; performing reduced pressure distillation on the lower organic phase after brine wash, standing and layering; and after dichloroethane is distilled off, dripping ethanol into the residual organic phase, and drying at 85-95 DEG C after suction filtration to obtain the butadiene bromide copolymer product. The product produced by the method is environment-friendly and nontoxic.
Description
Technical field
The present invention relates to the fire retardant technical field, relate in particular to a kind of method of producing butadiene bromide copolymer.
Background technology
The ultimate production of the whole world six large general superpolymer has reached 1.8 hundred million ton/years at present, wherein have 8～9% namely 1,400 ten thousand～1,500 ten thousand ton/years by fire-retardant, and its ratio will be more and more higher also, particularly at the E﹠E industry plastics, have approximately now 18% by fire-retardant, future can reach 23～25% in 5 years.
In addition, the fire-retardant ratio of engineering plastics is higher than general-purpose plastics, and 2007～2008 years, the ultimate production of global engineering plastics was 6,000,000 ton/years, wherein has 35% for flame retardant products, and it is higher to be used for the fire-retardant ratio of engineering plastics of electronics-electric industry.
With regard to global range, in the flame retarded polymeric material, plastics account for 80%, and textiles accounts for 5%, and rubber accounts for 10%, coating 3%, and paper and timber account for 2%.
The maximum user of fire retardant material is the industries such as electric, precision optical machinery, building materials, transportation (aircraft, train, automobile etc.), furniture, weaving.
Along with the fire safety standard of domestic and international increasingly stringent and the rapid growth of quantity of plastics, the market of global fire retardant showed a rising trend in recent years.Fire retardant has become one of important auxiliary agent of plastic working now, and with regard to output and consumption, it has become the additives for plastics that is only second to softening agent at present.
At present, in the product structure of China's fire retardant, chlorine-based flame retardant accounts for 69% of ultimate production, and bromide fire retardant accounts for 12%, and inorganic system accounts for about 17% of fire retardant.Compare with external structure, our chlorine is shared larger, and inorganic machine system and bromine are that proportion is excessively low.Bromine system and halophosphoric acid veriety are few, yield poorly, and hexabromocyclododecane (HBCD) is a kind of fire retardant, owing to its broad-spectrum high efficacy and by the countries in the world widespread use.But HBCD has one or more biological accumulations, on the toxicity of waterplant and on the persistence of sublimity impact, cause the application of alternative this product of a kind of brand-new environmental protection fire retarding agent of needs.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of producing the butadiene bromide copolymer of, environmental sound nontoxic to waterplant, environmental protection.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of method of producing butadiene bromide copolymer, at first ethylene dichloride is joined in the reactor, add afterwards butadienecopolymer (do not retrieve please and represent with the Chinese character title) under the restir state, stirring at normal temperature 25～35 minutes, then drip propyl carbinol in the reactor and stir, in 20～41 ℃ of downhill reaction stills, drip bromine afterwards, then be warming up to 40～42 ℃ of insulation reaction 13～17 hours, afterwards reacted material is carried out alkali cleaning, and stir standing demix after 8～12 minutes, then the organic phase with the lower floor behind the alkali cleaning standing demix stirs, wash afterwards, the organic phase of the lower floor behind the standing demix after the washing is stirred salt wash rear standing demix, lower floor's organic phase of then salt being washed behind the standing demix is carried out underpressure distillation, steam ethylene dichloride after, in remaining organic phase, drip ethanol, obtain described butadiene bromide copolymer product 85～95 ℃ of lower dryings behind the suction filtration.
The ethylene dichloride consumption that adds in the described reactor is 555～655 weight parts, and the butadienecopolymer consumption is 43～53 weight parts, and the propyl carbinol consumption is 147～167 weight parts, and the bromine consumption is 102.9～122.9 weight parts.
As preferred technical scheme, the mass concentration of described alkali cleaning employing 180～220 weight parts is 20% aqueous solution of sodium bisulfite.
As preferred technical scheme, the water of 180～220 weight parts is adopted in described washing.
As preferred technical scheme, described salt is washed the saturated aqueous common salt that adopts 180～220 weight.
As preferred technical scheme, the ethylene dichloride that described distillation steams is 280～320 weight parts.
As preferred technical scheme, described ethanol consumption is 520～620 weight parts.
As to improvement of the technical scheme, the filtrate that obtains behind the described suction filtration is reclaimed.
Product quality indicator such as following table that the present invention produces:
| Project | Quality index |
| Outward appearance | Off-white powder or particle |
| Bromine content (%) | ≥61 |
| Softening temperature (℃) | 190～205 |
| Fugitive constituent (%) | ≤0.3 |
| 5％WLT(℃) | 225～235 |
Owing to adopted technique scheme: a kind of method of producing butadiene bromide copolymer, at first ethylene dichloride is joined in the reactor, add butadienecopolymer under the restir state afterwards, stirring at normal temperature 25～35 minutes, then drip propyl carbinol in the reactor and stir, in 20～41 ℃ of downhill reaction stills, drip bromine afterwards, then be warming up to 40～42 ℃ of insulation reaction 13～17 hours, afterwards reacted material is carried out alkali cleaning, and stir standing demix after 8～12 minutes, then the organic phase with the lower floor behind the alkali cleaning standing demix stirs, wash afterwards, the organic phase of the lower floor behind the standing demix after the washing is stirred salt wash rear standing demix, lower floor's organic phase of then salt being washed behind the standing demix is carried out underpressure distillation, after steaming ethylene dichloride, in remaining organic phase, drip ethanol, obtain described butadiene bromide copolymer product 85～95 ℃ of lower dryings behind the suction filtration; The product environment-protecting asepsis that the method is produced accords with the demands of the market.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment one:
A kind of method of producing butadiene bromide copolymer:
The 555kg ethylene dichloride is dropped in the 1000L reactor, open step-down gear, under agitation add the 43kg butadienecopolymer in reactor, stirring at normal temperature 25 minutes makes its whole dissolvings.
In reactor, drip the 147kg propyl carbinol, stir.
Drip the 102.9kg bromine in reactor, the control temperature is 20 ℃ in the dropping process, and rate of addition can be seen as one sees fit control of temperature.
Be warming up to 40 ℃, insulation 17h.
Alkali cleaning; During material is transferred to and in the still, add the 180kg mass concentration and be 20% sodium sulfite solution, stirred standing demix 8 minutes.
Washing; Lower floor's organic phase is transferred in the washing kettle, adds 180kg water, stir washing, standing demix
Salt is washed; Lower floor's organic phase is transferred to salt washes in the still, add the 180kg saturated aqueous common salt, stir standing demix.
Distillation; Lower floor's organic phase is transferred in the still kettle, and underpressure distillation steams the 280kg ethylene dichloride.
Under agitation drip 520kg ethanol in still, it is slow that rate of addition begins to want, and the back can be accelerated.
Suction filtration reclaims filtrate.
Drying, 85 ℃ of oven dry obtain the butadiene bromide copolymer product.
Embodiment two:
A kind of method of producing butadiene bromide copolymer:
605kg (480L) ethylene dichloride is dropped in the 1000L reactor, open step-down gear, under agitation add the 48kg butadienecopolymer in reactor, stirring at normal temperature 30 minutes makes its whole dissolvings.
In reactor, drip 157kg (176L) propyl carbinol, stir.
Drip 112.9kg (36.2L) bromine in reactor, the control temperature is 30 ℃ in the dropping process, and rate of addition can be seen as one sees fit control of temperature.
Be warming up to 41 ℃, insulation 15h.
Alkali cleaning; During material is transferred to and in the still, add the 200kg mass concentration and be 20% sodium sulfite solution (40 sodium bisulfites are dissolved in 160kg water), stirred standing demix 10 minutes.
Washing; Lower floor's organic phase is transferred in the washing kettle, adds 200kg water, stir washing, standing demix
Salt is washed; Lower floor's organic phase is transferred to salt washes in the still, add the 200kg saturated aqueous common salt, stir standing demix.
Distillation; Lower floor's organic phase is transferred in the still kettle, and underpressure distillation steams the 300kg ethylene dichloride.
Under agitation drip 570kg ethanol in still, it is slow that rate of addition begins to want, and the back can be accelerated.
Suction filtration reclaims filtrate.
Drying, 90 ℃ of oven dry obtain the butadiene bromide copolymer product.
Embodiment three:
The 655kg ethylene dichloride is dropped in the 1000L reactor, open step-down gear, under agitation add the 48kg butadienecopolymer in reactor, stirring at normal temperature 35 minutes makes its whole dissolvings.
In reactor, drip the 167kg propyl carbinol, stir.
Drip the 122.9kg bromine in reactor, the control temperature is 41 ℃ in the dropping process, and rate of addition can be seen as one sees fit control of temperature.
Be warming up to 42 ℃, insulation 13h.
Alkali cleaning; During material is transferred to and in the still, add the 220kg mass concentration and be 20% sodium sulfite solution, stirred standing demix 12 minutes.
Washing; Lower floor's organic phase is transferred in the washing kettle, adds 220kg water, stir washing, standing demix
Salt is washed; Lower floor's organic phase is transferred to salt washes in the still, add the 220kg saturated aqueous common salt, stir standing demix.
Distillation; Lower floor's organic phase is transferred in the still kettle, and underpressure distillation steams the 320kg ethylene dichloride.
Under agitation drip 620kg ethanol in still, it is slow that rate of addition begins to want, and the back can be accelerated.
Suction filtration reclaims filtrate.
Drying, 90 ℃ of oven dry obtain the butadiene bromide copolymer product.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in above-described embodiment and the specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
All from the present invention is to devise, the structural transformation of having done without creative work all drops within protection scope of the present invention.
Claims (3)
1. a method of producing butadiene bromide copolymer is characterized in that, the 555kg ethylene dichloride is dropped in the 1000L reactor, opens step-down gear, under agitation adds the 43kg butadienecopolymer in reactor, and stirring at normal temperature 25 minutes makes its whole dissolvings; In reactor, drip the 147kg propyl carbinol, stir; Drip the 102.9kg bromine in reactor, the control temperature is 20 ℃ in the dropping process, and rate of addition is seen as one sees fit control of temperature; Be warming up to 40 ℃, insulation 17h; Alkali cleaning; During material is transferred to and in the still, add the 180kg mass concentration and be 20% sodium sulfite solution, stirred standing demix 8 minutes; Washing; Lower floor's organic phase is transferred in the washing kettle, adds 180kg water, stir washing, standing demix; Salt is washed; Lower floor's organic phase is transferred to salt washes in the still, add the 180kg saturated aqueous common salt, stir standing demix; Distillation; Lower floor's organic phase is transferred in the still kettle, and underpressure distillation steams the 280kg ethylene dichloride; Under agitation drip 520kg ethanol in still, it is slow that rate of addition begins to want, and accelerate the back; Suction filtration reclaims filtrate; Drying, 85 ℃ of oven dry obtain the butadiene bromide copolymer product.
2. a method of producing butadiene bromide copolymer is characterized in that, the 605kg ethylene dichloride is dropped in the 1000L reactor, opens step-down gear, under agitation adds the 48kg butadienecopolymer in reactor, and stirring at normal temperature 30 minutes makes its whole dissolvings; In reactor, drip the 157kg propyl carbinol, stir; Drip the 112.9kg bromine in reactor, the control temperature is 30 ℃ in the dropping process, and rate of addition is seen as one sees fit control of temperature; Be warming up to 41 ℃, insulation 15h; Alkali cleaning; During material is transferred to and in the still, add the 200kg mass concentration and be 20% sodium sulfite solution, stirred standing demix 10 minutes; Washing; Lower floor's organic phase is transferred in the washing kettle, adds 200kg water, stir washing, standing demix; Salt is washed; Lower floor's organic phase is transferred to salt washes in the still, add the 200kg saturated aqueous common salt, stir standing demix; Distillation; Lower floor's organic phase is transferred in the still kettle, and underpressure distillation steams the 300kg ethylene dichloride; Under agitation drip 570kg ethanol in still, it is slow that rate of addition begins to want, and accelerate the back; Suction filtration reclaims filtrate; Drying, 90 ℃ of oven dry obtain the butadiene bromide copolymer product.
3. method of producing butadiene bromide copolymer is characterized in that: the 655kg ethylene dichloride is dropped in the 1000L reactor, open step-down gear, under agitation add the 48kg butadienecopolymer in reactor, stirring at normal temperature 35 minutes makes its whole dissolvings; In reactor, drip the 167kg propyl carbinol, stir; Drip the 122.9kg bromine in reactor, the control temperature is 41 ℃ in the dropping process, and rate of addition is seen as one sees fit control of temperature; Be warming up to 42 ℃, insulation 13h; Alkali cleaning; During material is transferred to and in the still, add the 220kg mass concentration and be 20% sodium sulfite solution, stirred standing demix 12 minutes; Washing; Lower floor's organic phase is transferred in the washing kettle, adds 220kg water, stir washing, standing demix; Salt is washed; Lower floor's organic phase is transferred to salt washes in the still, add the 220kg saturated aqueous common salt, stir standing demix; Distillation; Lower floor's organic phase is transferred in the still kettle, and underpressure distillation steams the 320kg ethylene dichloride; Under agitation drip 620kg ethanol in still, it is slow that rate of addition begins to want, and accelerate the back; Suction filtration reclaims filtrate; Drying, 90 ℃ of oven dry obtain the butadiene bromide copolymer product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110049108 CN102174149B (en) | 2011-02-25 | 2011-02-25 | Method for producing butadiene bromide copolymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110049108 CN102174149B (en) | 2011-02-25 | 2011-02-25 | Method for producing butadiene bromide copolymer |
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| CN102174149B true CN102174149B (en) | 2013-04-10 |
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| CN103059367B (en) * | 2012-12-21 | 2015-07-08 | 山东润科化工股份有限公司 | Production method of brominated butadiene styrene rubber |
| CN106947007A (en) * | 2017-04-21 | 2017-07-14 | 天津天盈新型建材有限公司 | A kind of bromination high molecular weight flame retardant and preparation method thereof |
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| CN101501076A (en) * | 2006-08-16 | 2009-08-05 | 陶氏环球技术公司 | Process for brominating butadiene/vinyl aromatic copolymers |
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Date of cancellation: 20211223 Granted publication date: 20130410 Pledgee: Weifang Chengxin Financing Guarantee Co.,Ltd. Pledgor: SHANDONG RUNKE CHEMICAL Co.,Ltd. Registration number: Y2021980001500 |
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Denomination of invention: Method for producing brominated butadiene copolymer Effective date of registration: 20211229 Granted publication date: 20130410 Pledgee: Weifang Chengxin Financing Guarantee Co.,Ltd. Pledgor: SHANDONG RUNKE CHEMICAL Co.,Ltd. Registration number: Y2021980016928 |