Background technology
The ultimate production of current global six large general superpolymer has reached 1.8 hundred million tons/year, wherein have 8 ~ 9% that is 1,400 ten thousand ~ 1,500 ten thousand tons/year add fire retardant, and its ratio also will be more and more higher, particularly at electronics ~ electrical industry plastics, about have 18% to add fire retardant now, estimate reach 23 ~ 25% in the five-year.
In addition, the fire-retardant ratio of engineering plastics is higher than general-purpose plastics, 2007 ~ 2008 years, and the ultimate production of global project plastics is 6,000,000 tons/year, wherein has 35% for flame retardant products, and higher for the fire-retardant ratio of the engineering plastics of electronics ~ electrical industry.
With regard to global range, in 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 industry such as electric, precision optical machinery, building materials, transport (aircraft, train, automobile etc.), furniture, weaving.
Along with the fire safety standard of domestic and international increasingly stringent and the quick growth of quantity of plastics, the market of global fire retardant showed a rising trend in recent years.Fire retardant is one of important auxiliary agent having become plastic working now, and with regard to output and consumption, it has become the additives for plastics being 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, larger shared by our chlorine system, inorganic machine system and bromine system proportion too low.Bromine system and halophosphoric acid veriety few, yield poorly, hexabromocyclododecane (HBCD) is a kind of fire retardant, due to its broad-spectrum high efficacy by countries in the world widespread use.But HBCD has one or more biological accumulations, on the toxicity of waterplant and the persistence on sublimity impact, causes a kind of brand-new environmental protection fire retarding agent of needs to substitute the application of this product.
The report of bromination styrene-butadiene rubber(SBR) current also not this product at home, the related products of main research is abroad the synthesis of brominated butadiene homopolymer (Br ~ PBD), but the said products poor heat stability, be not enough to alternative hexabromocyclododecane.Enough thermostabilitys lack the application preventing the said products.But bromination styrene-butadiene rubber(SBR) has all advantages of the said products, thermostability is better than hexabromocyclododecane simultaneously, fully can substitute the application of hexabromocyclododecane.
Summary of the invention
The invention provides a kind of production method of bromination styrene-butadiene rubber(SBR), this production technique has the advanced features such as production technology environmental protection, energy consumption is few, product yield is high, steady quality is up to standard, operative technique is simple and safe.
Technical scheme of the present invention is achieved in that a kind of production method of bromination styrene-butadiene rubber(SBR), comprises the following steps:
(1) join in reactor by the ethylene dichloride of 555 ~ 655 weight parts, add the styrene-butadiene rubber(SBR) of 43 ~ 53 weight parts afterwards under whipped state, stirring at normal temperature is dissolved;
(2) bromizating agent of 302.9 ~ 322.9 weight parts is added halohydrocarbon to dissolve, obtain bromizating agent solution, then bromizating agent solution is added drop-wise in reactor, be warming up to 75 ~ 85 DEG C of backflow insulation reaction;
(3) material obtained after step (2) being reacted carries out alkali cleaning, by liquid system furnishing strong basicity, keep pH > 14, and stir stratification after 8 ~ 12 minutes, then isolate the organic phase of lower floor, and the organic phase after being separated is stirred 20 minutes;
(4) organic layer of step (3) gained is washed, stir stratification after 20 minutes, separate organic layer;
(5) organic layer of step (4) gained is carried out salt to wash, stir stratification after 20 minutes, separate organic layer;
(6) in the organic layer of step (5) gained, add emulsifying agent and water, then heating up distills out ethylene dichloride, then suction filtration, washing;
(7) by step (6) gained dry materials, described bromination styrene-butadiene rubber(SBR) is obtained.
Wherein, preferably, described bromizating agent is tetrabutylammonium tribromide, tetrabromo cyclic ketones, excessively bromine type quaternary ammonium salt or bromo-succinimide; Described halohydrocarbon is ethylene dichloride or tetracol phenixin.
Wherein, preferably, the churning time in described step (1) is 30 ~ 40 minutes.
Wherein, preferably, in described step (2), bromizating agent dropping temperature is 40 DEG C ~ 50 DEG C; The insulation reaction time is 15 ~ 25 hours.
Wherein, preferably, 15% ~ 30% aqueous solution of sodium bisulfite is adopted to carry out alkali cleaning in described step (3).
Wherein, preferably, in described step (5), the saturated nacl aqueous solution of employing 180 ~ 220 weight part washed by salt.
Wherein, preferably, in described step (6), emulsifying agent is sodium laurylsulfonate, alkylphenol polyoxyethylene class, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether series or styroyl phenol polyethenoxy ether.
Wherein, preferably, in described step (6), the weight ratio of emulsifying agent and water is 1:20 ~ 1:10.
Wherein, preferably, the temperature distilling out ethylene dichloride in described step (6) is 90 ~ 100 DEG C
Polyoxyethylene nonylphenol ether series is condensation compound of alkyl phenol and epoxy ethane, and specification has OP ~ 4,7,9,10,13,15,20,30,40,50.
Bromination styrene-butadiene rubber(SBR), the environmental sound nontoxic to waterplant adopting the present invention to produce, environmental protection.Bromination styrene-butadiene rubber(SBR) provided by the invention is adopted production method and is had the features such as production technology environmental protection, energy consumption is few, product yield is high, steady quality is up to standard, operative technique is simple and safe.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The production method of bromination styrene-butadiene rubber(SBR) provided by the invention, comprises the following steps:
(1) join in reactor by the ethylene dichloride of 555 ~ 655 weight parts, add the styrene-butadiene rubber(SBR) of 43 ~ 53 weight parts afterwards under whipped state, stirring at normal temperature is dissolved;
(2) bromizating agent of 302.9 ~ 322.9 weight parts is added halohydrocarbon to dissolve, obtain bromizating agent solution, then bromizating agent solution is added drop-wise in reactor, be warming up to 75 ~ 85 DEG C of backflow insulation reaction;
(3) material obtained after step (2) being reacted carries out alkali cleaning, by liquid system furnishing strong basicity, keep pH > 14, and stir stratification after 8 ~ 12 minutes, then isolate the organic phase of lower floor, and the organic phase after being separated is stirred 20 minutes;
(4) organic layer of step (3) gained is washed, stir stratification after 20 minutes, separate organic layer;
(5) organic layer of step (4) gained is carried out salt to wash, stir stratification after 20 minutes, separate organic layer;
(6) in the organic layer of step (5) gained, add emulsifying agent and water, then heating up distills out ethylene dichloride, then suction filtration, washing;
(7) by step (6) gained dry materials, described bromination styrene-butadiene rubber(SBR) is obtained.
Step (4) and step (6) washing its objective is the water-soluble impurity washed away in material, and its consumption can be determined according to practical situation.
The ethylene dichloride steamed in step (6) carries out recovery recycled, and the filtrate obtained after suction filtration is reclaimed.
Embodiment 1
Dropped into by 555kg ethylene dichloride in 1000L reactor, open stirrer, under agitation in reactor, add 48kg styrene-butadiene rubber(SBR), stirring at normal temperature 35 minutes, makes it all dissolve.
In reactor, drip 302.9kg tetrabutylammonium tribromide (being dissolved in ethylene dichloride), control temperature 40 DEG C in dropping process, rate of addition can see that temperature takes the circumstances into consideration to control.
Be warming up to 80 DEG C, backflow insulation reaction 17h.
Alkali cleaning: during material is transferred to and in still, adds the sodium sulfite solution that 180kg mass concentration is 20%, stir 8 minutes, stratification, pH value > 14.
Washing: lower floor's organic phase is transferred in washing kettle, adds 180kg water, stir washing in 20 minutes, stratification.
Salt is washed: lower floor's organic phase is transferred to salt and washes in still, add 180kg saturated nacl aqueous solution, stirs 20 minutes, stratification.
Distillation: lower floor's organic phase is transferred in still kettle, adds 120kg water and the underpressure distillation of 6kg sodium laurylsulfonate, be warming up to 90 DEG C and steam 550kg ethylene dichloride.
Suction filtration: filtrate is reclaimed filter cake 180kg and wash suction filtration again.
Dry: 85 DEG C of oven dry obtain bromination styrene-butadiene rubber(SBR) 140.1kg, product yield 93.4%, and through Product checking, product purity is 96.8%.
Embodiment 2
Dropped into by 605kg ethylene dichloride in 1000L reactor, open stirrer, under agitation in reactor, add 48kg styrene-butadiene rubber(SBR), stirring at normal temperature 40 minutes, makes it all dissolve.
In reactor, drip 350kg bromo-succinimide (being dissolved in ethylene dichloride), control temperature 50 DEG C in dropping process, rate of addition can see that temperature takes the circumstances into consideration to control.
Be warming up to 80 DEG C, backflow insulation reaction 15h.
Alkali cleaning: during material is transferred to and in still, adds the sodium sulfite solution (40kg sodium bisulfite is dissolved in 160kg water) that 200kg mass concentration is 20%, stir 10 minutes, stratification, pH value > 14.
Washing: lower floor's organic phase is transferred in washing kettle, adds 200kg water, stir washing in 20 minutes, stratification.
Salt is washed: lower floor's organic phase is transferred to salt and washes in still, add 200kg saturated nacl aqueous solution, stirs 20 minutes, stratification.
Distillation: lower floor's organic phase is transferred in still kettle, adds 200kg water and the underpressure distillation of 10kg polyoxyethylene nonylphenol ether ~ 10, steam 595kg ethylene dichloride.
Suction filtration: filtrate is reclaimed filter cake 180kg and wash suction filtration again.
Dry: 85 DEG C of oven dry obtain bromination styrene-butadiene rubber(SBR) 145.5kg, product yield 97.0%, and through Product checking, product purity is 98.5%%.
Embodiment 3
Dropped into by 655kg ethylene dichloride in 1000L reactor, open stirrer, under agitation in reactor, add 48kg styrene-butadiene rubber(SBR), stirring at normal temperature 35 minutes, makes it all dissolve.
In reactor, drip 305kg tetrabromo cyclic ketones (being dissolved in ethylene dichloride), control temperature 45 DEG C in dropping process, rate of addition can see that temperature takes the circumstances into consideration to control.
Be warming up to 80 DEG C, backflow insulation reaction 20h.
Alkali cleaning: during material is transferred to and in still, adds the sodium sulfite solution that 220kg mass concentration is 20%, stir 12 minutes, stratification, pH value > 14.
Washing: lower floor's organic phase is transferred in washing kettle, adds 220kg water, stir washing in 20 minutes, stratification.
Salt is washed: lower floor's organic phase is transferred to salt and washes in still, add 220kg saturated nacl aqueous solution, stirs 20 minutes, stratification.
Distillation: lower floor's organic phase is transferred in still kettle, adds 500kg water and the underpressure distillation of 50kg polyoxyethylene nonylphenol ether ~ 10, steam 645kg ethylene dichloride.
Suction filtration: filtrate is reclaimed filter cake 180kg and wash suction filtration again.
Dry: 85 DEG C of oven dry obtain bromination styrene-butadiene rubber(SBR) 144.9kg, product yield 96.6%, and through Product checking, product purity is 95.2%.
Three embodiment gained sample detection results are: