CN1122046C - Process for the preparation of brominated polystyrene having improved color characteristics - Google Patents
Process for the preparation of brominated polystyrene having improved color characteristics Download PDFInfo
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- CN1122046C CN1122046C CN97182452A CN97182452A CN1122046C CN 1122046 C CN1122046 C CN 1122046C CN 97182452 A CN97182452 A CN 97182452A CN 97182452 A CN97182452 A CN 97182452A CN 1122046 C CN1122046 C CN 1122046C
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Abstract
The present invention relates to a process for preparing brominated polystyrene used as an additive for endowing a polymer matrix with fire retardance. The process comprises the steps that a solution of a polystyrene reactant in a halogenated hydrocarbon solvent is prepared, and the solution contains of 5% or so to 20% (weight) or so of polystyrene reactant; a lewis acid brominated catalyst is added to form the solution; 1 or so to 3.3 mole or so of brominating agent is added into the solution according to each mole polystyrene repeating unit; the polystyrenes reactant and the brominating agent react at the reaction temperature minus 20 DEG C or so to 50DEGC or so; the process comprises has improvement for controlling the color characteristics of the obtained brominated polystyrene product. In the improvement process, the polystyrene reactant with the average molecular weight of 500 or so to 1, 500, 000 or so is selected; the effective catalyzing amount of the catalyst is selected on the basis that sufficient intensity is supplied to cause the polystyrene to carry out at least one-step bromination reaction but the polystyrene can not be alkylated due to a halogenated hydrocarbon solvent; the brominating agent is selected from bromine chloride and bromine; operation is carried out at minimum possible temperature in the range according to the selected brominating agent and the catalyst; the brominated polystyrene is separated; the color characteristics of the obtained brominated product are improved by the selection and the research of reaction time and temperature, the catalyst, the brominating agent and a product separation process.
Description
Technical field
The present invention relates generally to and have the brominated Polystyrene that improves color characteristics.More particularly, the present invention relates to make the method for polystyrene bromination, thereby obtain having the brominated Polystyrene that improves color characteristics with bromizating agent, catalyzer, reaction times, separation method and temperature controlled unique combination.
Background of invention
It is known with the prior art of flame retardant resistance that brominated Polystyrene can be given polymkeric substance.For example, at United States Patent (USP) 3,474, in 067, described many brominated Polystyrenes and done the application of the flame-retardant additive of polyolefin-based moulding material, this patent has been described based on polyethylene and the polypropylene nuclear brominated Polystyrene different with several together with for example moulding material combination of ANTIMONY TRIOXIDE SB 203 99.8 PCT of synergistic agent.Lay special stress on uses poly--(tribromo-benzene ethene).Shown in this patent table 1.Yet, the molecular weight of this patent and unexposed brominated Polystyrene, also unexposed how producing.
United States Patent (USP) 3,975,354 described burn-resisting and thermoplastic, glass fibre enhanced polyester molding compounds, contain poly-(2,4,6-tribromo-benzene ethene) composition of saturated polyester, synergistic agent and 3%～30% (weight).It is commercially available product that this patent has been delivered poly-(2,4,6-tribromo-benzene ethene), and its density is 2.3g/cm
3, bromine content is 69%.But the method for the described product of the undeclared production of this patent.
English Patent 364873 has been described in the presence of iron(ic) chloride or aluminum chloride, directly examines polystyrene in the halogenated solvent with elemental chlorine.
The direct bromination of polystyrene is described in United States Patent (USP) 3,050, in 476.In the presence of bromine, with the suspension heating of granules of polystyrene, so that bromine and polymer beads Chemical bond.The bromine amount that adds is to the very low degree of bromination.
United States Patent (USP) 3,845,146 have described for example bromination of low alkyl group benzene of aromatic substance, adopt catalyzer such as aluminum chloride, and bromine chloride is made bromizating agent.Be reflected under the automatic pressure, scope is about 50～100psig usually, carries out in closed reaction vessel.
Cubbon and Smith exist
Polymer,
10, in one piece of paper of 479-487 (1969), the cinnamic synthetic and polymerization of tribromo has been described.Tribromo-benzene ethene can divide the polystep reaction preparation, at first, hydrogen bromide is added on the cinnamic pair of key, to generate 2 bromoethyl benzene, then, this material is reacted with elemental bromine in the presence of iron(ic) chloride, and bromine is introduced in the nuclear.Subsequently under about 30 ℃, by with the reaction of potassium ethylate, remove hydrogen bromide, introduce two keys again.This product turns out to be 2,4 by nuclear magnetic resonance spectrum, 5-tribromo-benzene ethene.In 30 ℃ benzole soln, observe the cinnamic rate of polymerization of this tribromo.With the comparison of doing of its rate of polymerization and Dowspray 9, the conclusion that draws is the polymerization that the introducing of bromine atoms has activated vinyl, and the cinnamic rate of polymerization of tribromo is fast than Dowspray 9, and the rate of polymerization of Dowspray 9 is fast than vinylbenzene successively.
At German Patent 1,570, in 395, embodiment 2 illustrates the production of poly--(2,4,6-tribromo-benzene ethene) to the effect that, and embodiment 4 only describes the production of poly--(tribromo-benzene ethene) to the effect that.
Some other patents of having issued have been described the production of brominated Polystyrene oligopolymer and the utilization of flame retardant resistance.These oligopolymer can make by elemental bromine and the reaction of hydrogenated polystyrene oligopolymer, as people such as Naarmann at United States Patent (USP) 4,074,033 and 4, described in 143,221, wherein used catalyzer is aluminum chloride (lewis acid catalyst), perhaps use another kind of method, the polyreaction by brominated styrene makes.
At United States Patent (USP) 4,107, described this class brominated oligomer in 231 and be applicable to and give linear polyester flame retardant resistance.The polymerization degree scope of oligopolymer is 3～20.This patent has also been mentioned the purposes of tribromide oligopolymer.
At United States Patent (USP) 4,137, in 212, disclosed the polymerization degree and be 3～90 similar brominated Polystyrene oligopolymer, be applicable to fire prevention molding nylon composite.This patent has also been mentioned the tribromide oligopolymer.
At United States Patent (USP) 4,151, in 223, brominated oligomer has 3～about 100 the polymerization degree, and has described it and be applicable to and give linear thermoplastic's trevira and filament flame retardant resistance.This piece patent also points out, halogenation low polystyrene or chlorating or bromination, its halogenation degree can reach four corner.
United States Patent (USP) 4,352,909 have described the preparation of tribromide poly styrene polymer.This method uses bromine chloride as bromizating agent, and therefore 1～2% (weight) of this product is chlorine usually.
United States Patent (USP) 4,200,703 disclose a kind of method for preparing the nuclear brominated Polystyrene of thermostability.This method is included in lewis acid catalyst and lewis acidic nucleophile exists down, make the polystyrene that is dissolved in the chlorinated hydrocarbon, under-20 ℃～40 ℃ temperature, carry out bromination with bromine chloride or bromine, nucleophile can play the effect of Lewis base such as water, and its consumption is that per 1 mole of lewis acid catalyst uses 0.02～2 mole.This method can prepare the high-molecular weight product, needn't make polystyrene raw material carry out hydrogenation.Its product is no crosslinked usually.But the color gamut of solid product is extremely light yellow to " white " from reddish brown brown to light beige.
European patent application 0201411 discloses a kind of United States Patent (USP) 4,200 that is similar to, 703 brominated Polystyrene, and wherein polystyrene is anionoid polymerization, the polymerization degree is greater than 400.
When brominated Polystyrene was used as flame-retardant additive in thermoplastics, its color was primary character concerning the producer of thermoplastic material.The producer of thermoplastics wishes to produce the very wide thermoplastic articles of color gamut.Painted additive color is dark more, and then it is difficult to mate the color of (generation) wide ranges more.Painted additive color is shallow more, and then it is easy to produce the color of wide ranges more.Therefore, consider thermoplastics parts manufacturer's needs, with consider that existing method is unsuitable for being used for making the brominated Polystyrene with required light characteristic, therefore, there are a kind of like this needs, promptly produce the brominated Polystyrene with improved light outward appearance, consequently final user can make the color of wide scope, and therefore can satisfy the needs and the requirement in market better.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of brominated Polystyrene that improves color characteristics that has.
Another object of the present invention provides a kind of method, and this method makes the operator can select various reaction components and reaction parameter, to obtain to have the brominated Polystyrene of the best color characteristics that is suitable for selecting among variable.
It is to determine influential various reagents of the color characteristics that is obtained in the bromination reaction of polystyrene and reaction parameter that the present invention has a purpose again.
At least one or a plurality of purpose in the above-mentioned purpose exceed the advantage of prior art together with them, will be more obvious according to following specification sheets, and as hereinafter illustrated with required for protection, above-mentioned purpose and advantage are to realize by means of the present invention.
For achieving the above object, the Preparation of Brominated Polystyrene method that the present invention's first scheme provides, the solution in the hydrocarbon solvent, this solution contain the described polystyrene reactant agent of 5%～20 weight %;
Add weak Lewis acid bromination catalyst to form solution; The content of catalyzer is 0.2-10 (weight) %;
Add 1～3.3 mole bromizating agent in the described solution by each mole polystyrene repeating unit, described bromizating agent is selected from bromine chloride and bromine;
Reaction is 1-20 hour under-20 ℃～50 ℃ temperature, makes the reaction of described polystyrene and described bromizating agent obtain the reaction product brominated Polystyrene;
The reaction product isolated brominated Polystyrene finally obtains the improved brominated Polystyrene of color characteristics.
The Preparation of Brominated Polystyrene method that alternative plan of the present invention provides is in first scheme, and described hydrocarbon solvent is selected from tetracol phenixin, chloroform, methylene dichloride, 1,2-ethylene dichloride, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, glycol dibromide and composition thereof.
The Preparation of Brominated Polystyrene method that third party's case of the present invention provides is in first scheme, further comprises the step with the described reaction of basic metal bisulfite salt brine solution quenching.
The Preparation of Brominated Polystyrene method that the cubic case of the present invention provides is in first scheme, and described catalyzer is selected from butter of antimony and antimony tribro-and composition thereof.
The Preparation of Brominated Polystyrene method that the present invention's the 5th scheme provides is in cubic case, and described separating step carries out in alkane alcohols that can precipitated product or ketone, and comprises the following steps:
Inclusion in the reaction vessel under agitation is added in the alkane alcohols or ketone of described energy precipitated product;
Precipitate described brominated polymer; With
Reclaim and dry described brominated polymer.
The Preparation of Brominated Polystyrene method that the present invention's the 6th scheme provides is in the 5th scheme, and described ketone is acetone.
The Preparation of Brominated Polystyrene method that the present invention's the 7th scheme provides is in the 5th scheme, and described catalyzer is a butter of antimony; Described bromizating agent is a bromine chloride; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
The Preparation of Brominated Polystyrene method that the present invention all directions case provides is in the 7th scheme, and described hydrocarbon solvent is 1, the 2-ethylene dichloride.
The Preparation of Brominated Polystyrene method that the present invention's the 9th scheme provides is in the 5th scheme, and described catalyzer is an antimony tribro-; Described bromizating agent is a bromine chloride; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
The Preparation of Brominated Polystyrene method that the present invention's the tenth scheme provides is in the 5th scheme, and described catalyzer is a butter of antimony; Described bromizating agent is a bromine; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
The Preparation of Brominated Polystyrene method that the present invention's the 11 scheme provides is in the 5th scheme, and described catalyzer is an antimony tribro-; Described bromizating agent is a bromine; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
The Preparation of Brominated Polystyrene method that the present invention's the 12 scheme provides is in cubic case, and described separating step is undertaken by flash distillation water, and comprises the following steps:
Under agitation the inclusion of reaction vessel is added in the boiling water and in the preparation slurry, flashes away described solvent and from described slurry, reclaim described brominated polymer.
The Preparation of Brominated Polystyrene method that the present invention's the 13 scheme provides is in the 12 scheme, and described catalyzer is a butter of antimony; Described bromizating agent is a bromine chloride; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
The Preparation of Brominated Polystyrene method that the present invention's the tenth cubic case provides is in the 12 scheme, and described catalyzer is an antimony tribro-; Described bromizating agent is a bromine chloride; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
The Preparation of Brominated Polystyrene method that the present invention's the 15 scheme provides is in the 12 scheme, and described catalyzer is a butter of antimony; Described bromizating agent is a bromine; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
The Preparation of Brominated Polystyrene method that the present invention's the 16 scheme provides is in the 12 scheme, and described catalyzer is an antimony tribro-; Described bromizating agent is a bromine; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
The Preparation of Brominated Polystyrene method that the present invention's the 17 scheme provides is in first scheme, and described polystyrene reactant agent is selected from homopolymerization polystyrene, polystyrene oligopolymer, halogenated polystyrene and alkylation polystyrene.
The described reaction times of embodiment is 5 hours.
The Preparation of Brominated Polystyrene method that the present invention's the tenth all directions case provides is in first scheme, and described polystyrene reactant agent is selected from homopolymerization polystyrene, polystyrene oligopolymer, halogenated polystyrene and alkylation polystyrene.
Embodiment
A preferred embodiment of the inventive method can be represented with following reaction formula:
(reaction formula 1)
Pointed as reaction formula 1, the reaction in this embodiment of the present invention normally at solvent, is carried out in the preferred chlorinated hydrocarbon solvent.Preferred solvent comprises halon, for example tetracol phenixin, chloroform, methylene dichloride, 1,2-ethylene dichloride, glycol dibromide, vinyl trichloride, sym.-tetrachloroethane or the like.Preferred solvent is EDC (1, the 2-ethylene dichloride).The mixture of solvent also can use.
At first the polystyrene reactant agent is dissolved in the solvent, generating concentration is about solution of 5～about 20% (weight).Add catalyzer then, add bromizating agent subsequently gradually, and allow the gained mixture effectively react under the temperature control.
Bromizating agent is selected from bromine chloride, elemental bromine or its mixture.Pure bromine chloride contains the bromine of about 70% (weight).Be practical purpose, use about 65～about 75% (weight) the bromine chloride of total bromine content.Although it is pure that bromizating agent preferably adds, the method for using can be used the solution of bromizating agent in the halon solvent, and described solvent can be identical with the polystyrene solvent for use, also can be different, but should be with it consistency.Each polystyrene repeating unit in every mole of polystyrene, adds about 2.8～about 3.3 moles bromizating agent, so that can obtain to be up to 3 bromines.More generally, the bromizating agent consumption is to be decided by bromination amount desired in polystyrene products, therefore, for making each polystyrene repeating unit reach 1～3 bromine, use 1～about 3.3 moles bromizating agent, back one quantity has been Duoed a bit than 3 moles of summaries, to guarantee the complete of bromination reaction.The relative quantity of bromine chloride and bromine is not restriction of the present invention in the mixture, but it defines somewhat with regard to bromination catalyst, will explain as following.
Catalyzer is weak Lewis acid halogenation catalyst, preferred butter of antimony or antimony tribro-.So-called " weak " should be appreciated that and be meant impossible catalysis friedel-crafts (Friedel-Crafts) alkylated reaction of described catalyzer, perhaps, in this specific system, be meant for example reaction of polystyrene of halon and aromatics base material.Under the situation of many halogenated solvents, a kind of like this reaction can cause undesirable crosslinking reaction.
Must use the effective catalytic amount of weak lewis acid catalyst.Catalyst content is that about 0.2～about 10% (weight) is expected.The accurate amount of catalyzer will depend on its activity.Concerning butter of antimony, use bromine chloride to make bromizating agent, in breadboard experiment, catalyst content is less than the decline that about 5% (weight) can cause speed of reaction, and generates and owe the product of bromination, unless use excessive a lot of bromine chloride.Surpass a lot of bromizating agent of theoretical aequum when reaching with very a spot of catalyzer, it is feasible being reflected at technical, on the other hand, when with a large amount of catalyzer and when surpassing seldom bromizating agent of theoretical aequum, the primary factor of decision catalyst levels is lewis acidic intensity.In other words, concerning stronger lewis acid catalyst, with more a small amount of, and with respect to more weak Lewis acid, with relatively large.
The catalyst mixture that can further control the lewis acid catalyst intensity that is used for method also is possible.This class mixture not only comprises two or more Lewis acids, but also can comprise the mixture that contains one or more Lewis bases, for example, but is not limited to water, alcohol, ether, ester, carboxylic acid, chloride of acid, ketone, aldehyde, amine, nitrile or the like.For various Lewis bases and acid are discussed more up hill and dale, visible United States Patent (USP) 4,200,703, its content is incorporated herein as a reference.For the selection of bromination catalyst or catalyst mixture, also be a kind of function of used special bromizating agent.Understand as those skilled in the art, for example bromine chloride is active stronger bromizating agent, therefore when using more weak catalyzer, might reach the bromination reaction of higher degree.And when using bromine, be necessary to use more active catalyzer, to reach the aromatics bromination reaction of higher level.When bromizating agent is the mixture of bromine chloride and bromine, make both any relative populations and selected catalyzer keep balance, vice versa, and those skilled in the art will be understood that this point.
Reaction between bromizating agent and the polystyrene reactant agent can be carried out under the arbitrary temperature in about-20 ℃～about 50 ℃ of scopes.Usually, for obtaining best color, the lower region of preferred range.But when low temperature, speed of reaction reduces, and in fact can not be industrial acceptable speed.Therefore, in order to obtain industrial acceptable response speed, with regard to temperature, be necessary to take the way of trading off.In the cut-and-try work of delivering hereinafter, 5 hours speed of reaction is considered to gratifying.We have also observed the influence that speed of reaction is subjected to selected bromizating agent and selected catalyzer.
Used polystyrene reactant agent or oligopolymer or polymkeric substance.Therefore, the starting molecule amount of polystyrene is about 500Mw～about 1,500,000Mw, and preferably about 500Mw～about 500,000Mw.The inventive method is for substituted polystyrene, and replacement is that the bromination reaction of nuclear is effective equally.Obviously, the nuclear substituting group will influence the position (many) of bromination reaction generation and the quantity of the more bromination reaction of generation.The method according to this invention, comprised halogenated and alkylating polymkeric substance by the example of the substituted polystyrene of bromination, for example poly--(bromostyrene), poly--(chlorostyrene), poly--(dichlorobenzene ethene), poly--(dibromo-benzene ethene), poly--(chloro-bromo-vinylbenzene), poly--(4-vinyl toluene) and poly--(list-low alkyl group vinylbenzene).Halogenic substituent comprises chlorine and bromine, and alkyl substituent comprises the low alkyl group that contains 1～about 4 carbon atoms.Therefore, in whole specification sheets and claims, used term polystyrene reactant agent or polystyrene only are with the substituted polystyrene that refers in aforesaid homopolymerization polystyrene and the oligopolymer and the scope of the invention.
Reaction is proceeded to introduce on each aromatic proton and be up to three bromine atoms.Hydrogenchloride and hydrogen bromide produce as the by product of reaction, and what this depended on use is bromine chloride or bromine.
Pointed as above-mentioned reaction formula I, mainly be the tribromide polystyrene although the present invention can be used to produce, method of the present invention generally also can be used for production and have any required bromination degree, is up to 3 brominated Polystyrene product.
Generally poorer aspect the existing bromination process that is used for styrene polymer or oligopolymer, the tinted material that is suitable in preparation than the effect of the inventive method.Use the preferred method of the present invention can produce the performance with fabulous color on any required bromination level, promptly the product of very slight color is the ideal flame-retardant additive when causing the height brominated product to be used for plastics industry.It is the product of tribromide reaction basically that the bromination degree is lower than, and making flame-retardant additive is effective equally.
For according to the present invention optimum implementation carry out reaction of the present invention, should select the polystyrene reactant agent to have weight-average molecular weight is about 500 or bigger, preferred 150,000 or bigger, the most about-20 ℃～about 50 ℃.Though reaction can be carried out at a lower temperature, speed is slower.Under comparatively high temps, also can carry out, but with the rising of temperature, the color variation of product.This reaction is heat release, therefore, cool off.When the color of product is significant consideration, and always the case, particularly with regard to the tribromide polystyrene products, it is believed that the temperature of the control reaction mixture of remaining valid is most important.But when bromizating agent adds, also want stirred reaction mixture for some time, so that reaction is carried out fully.
Though the reaction times part is according to temperature of reaction, so a kind of time can be done bigger change between about 1 hour～20 hours.When preferred catalyzer when being great or active, temperature of reaction or time, or the two, can reduce.When reaction can not fully be cooled to than low degree, can realize the control of p-poly-phenyl ethene additive color characteristics by the shortening reaction times.Be appreciated that the purpose of the present invention color that offers the best is possible, therefore in spiritual scope of the present invention, owing to considered bromination catalyst, bromizating agent and intermediate processing, so reaction times and temperature can both be determined and select.People also are appreciated that the longer or shorter reaction times of not necessarily eliminating, and the reaction time range that shows at first will satisfy the most receptible industrial timed interval.
After thinking that reaction finishes, any excessive bromizating agent is all destroyed, for example adds the aqueous solution of reductive agent such as basic metal hydrosulphite.Stop stirred reaction mixture then, and occur being separated.
Can use generally acknowledged and acceptable method, for example the water flash method and the non-solvent precipitator method are finished the recovery of product.In the non-solvent precipitator method, with can solubilizing reaction the organic solvent of the product mixed non-solvent that mixes, at room temperature be kept in the independent container.The non-solvent liquid that is suitable for comprises the alkane alcohols of energy precipitated product, particular methanol, or ketone, for example acetone.Inclusion in the reaction vessel under agitation slowly is added in the non-solvent.Under suitable condition, brominated polymer precipitates with fine grain form, by filtered and recycled and carry out drying.In the water flash method, the solution of product is added in the boiling water gradually, cause that solvent flashing falls, and product is stayed with the form of aqueous slurry.Reclaim product then according to a conventional method.
However, the method for product separation is a factor of control brominated product color characteristics equally.A kind of like this viewpoint of the investigation support of here delivering, promptly the non-solvent precipitator method surpass the water flash method as the other method that obtains better color.
In essence, the tribromide product be bromine content be at least 66% a kind of.Yet agent of the present invention flashes away, and product is stayed with the form of aqueous slurry.Reclaim product then according to a conventional method.
However, the method for product separation is a factor of control brominated product color characteristics equally.A kind of like this viewpoint of the investigation support of here delivering, promptly the non-solvent precipitator method surpass the water flash method as the other method that obtains better color.
In essence, the tribromide product be bromine content be at least 66% a kind of.Yet the inventive method is so a kind of method, when adopting bromizating agent to be bromine chloride, except the nuclear bromination takes place, some nuclear chlorinations can take place also.Therefore, in general, in this case, the bromine content of product is counted about 66%～about 69% (weight) by the weight of product, and typical cl content is about 0.5～1% (weight) of product, also can be up to about 2% (weight) of product.
Can find according to analyzing, by implementing the typical tribromide polystyrene product that preferred method makes, can contain to have an appointment 66%～about 69% (weight) bromine, the chlorine of about 0.5～2% (weight), and contain the volatile matter of about 0.2%～0.5% (weight) usually.If there are three bromine atoms to replace the yield that calculates reaction on the nuclear with each aromatic nucleus, the yield that method typical case then of the present invention produces is at least about 90% or higher.
When implementing preferred method, particularly on technical scale, within the scope of the invention,, can make many changes according to description to above-mentioned general method.For example, commercially available bromine chloride directly is added in the reactor, perhaps uses bromine chloride solution.Usually must use more excessive bromine chloride, but the amount that surpasses depends on reaction conditions, for example selection of the moisture in the solvent, catalyzer, temperature of reaction or the like.
Being selected the organic solvent of making reaction medium should be able to the solubilizing reaction agent, and should be inert or reactive low for reagent.Particularly suitable be halogenated those, chlorating aliphatic saturated hydrocarbon especially.For fear of the addition of halogen, the carbon that primary is in the solvent must be saturated.As noted above, the solvent that is suitable for comprises tetracol phenixin, chloroform, sym.-tetrachloroethane, methylene dichloride, 1,2-ethylene dichloride, vinyl trichloride, glycol dibromide or the like, and wherein EDC (1, the 2-ethylene dichloride) is preferred.If the use methylene dichloride should use suitable device to adorn it, because the boiling point of methylene dichloride is low, be easy to volatilization, so be tending towards overflowing.
When using the weak lewis acid catalyst of single body, solvent should be anhydrous basically, because water can destroy catalyzer or make catalyst deactivation.Usually, use the solvent of technical grade.In general, the producer stipulates maximum water content, and for this reason, finding to use the technical grade solvent is that other people is satisfied.Yet, find out that water content is wise sfgd., and if possible, by the azeotropic solvent drying.But, exist a spot of moisture in the common commercially available halon solvent, catalyst activity is slowed down and, thereby in some cases,, may need catalyzer more or less for reaching specified result, this depends on the Total Water of existence.
The product of any brominated Polystyrene all has the inherent flame retardant resistance.For the flame-retardant additive that main polymer uses, the additive of minimum viable quantities is only used in expectation usually.For this reason, preferably produce and use the higher flame-retardant additive polystyrene of brominated amount.Industrial, common way is the quantity of regulating used brominated additives in the plastics composite, to obtain the anti-calcination of degree of particularity.Usually, the bromine content of special additive is high more, and then its efficient is high more, and required additive is few more.In general, the amount of additives of use is few more, and is then economical more.Though under certain conditions, use fire retardant can improve some physicals of total composition.But, more generally, use additive can reduce desired physical properties,, when obtaining equivalent results, preferably use than minor amounts of additives for this reason.
Although it is to indicate to wish complete bromination at this in particular cases, do not have actual effect that these considerations be it seems.Specified as multiple confirmation of the present invention, when being used as 1 of solvent, when reaching 3 halogenation points in the 2-ethylene dichloride, halogenated polystyrene begins to form the separation phase.This variation and crosslinked irrelevant, but relevant with the solubleness appearance variation in using special solvent.This is separated, and makes that handling and reclaim product becomes difficult.For this reason, implement the preferred method of the present invention usually to produce three halogenated polystyrene products, promptly main is tribromide polystyrene product.
By setting forth concrete demonstration of the present invention, the present invention is done explanation in further detail.Embodiment below and all in the application, all umbers and per-cent all by weight, all temperature are all represented with centigradetemperature, unless tangible indication is arranged in addition.Used EDC solvent is with the azeotropic distillation or be dried to moisture with the molecular sieve drying method and be lower than 100ppm.
In 1 liter of resin flask of a pressure equilibrium feed hopper that mechanical stirrer, thermometer, spiral cooler and 500ml strap clamp cover be housed, add 50.1g (counting 0.481 mole) polystyrene and 350ml 1,2-ethylene dichloride (EDC) with the vinylbenzene repeating unit.In the solution of this stirring, add 0.5g (0.01096 mole) butter of antimony (adding), again solution is chilled to 20 ℃ with the solution 0.2g/ml in EDC.By 187.5g (1.625 moles) bromine chloride, the bromine chloride solution that 2.7g (0.0169 mole) bromine and 187.5g EDC form added in 3 hours in the polystyrene solution continuously, kept the bromination temperature at 20 ± 2 ℃ simultaneously.About more than two hours of general stirring system is 66% (total bromination time is 5 hours) so that can make bromine content in the final product reach minimum.
Add aqueous solution of sodium bisulfite 180g (20% (weight)), surpass 35 ℃ speed, the amount of deionized water identical with used aqueous solution of sodium bisulfite weight added in the mixture not make temperature.This mixture was stirred other 10～15 minutes, be transferred to then in 2 liters the separating funnel.
Tell after the organic layer, with 1 liter of fresh deionized water wash three times.In washing process for the third time, the pH of water layer is transferred to 7 by increasing progressively the saturated aqueous solution of sodium bisulfite that adds about 60g with it.After the washing, organic phase is put into sizable addition funnel for the third time.This is added in 3 liters of Morton resin flask that mechanical stirrer, distillation tower head, condenser, susceptor and heating mantles are housed.This flask also is equipped with 2 liters just by the boiling deionized water of vigorous agitation.When adding to solution in the boiling water, EDC is flashed with the form of EDC/ water azeotropic mixture.
In this operating process, temperature maintenance is between 91 ℃～100 ℃.After solution adds, the slurry that is generated further is incubated 1 hour down at about 100 ℃.
Filter and collect product, on strainer,, use 4 liters of cold deionized water wash again with the deionized water wash of 4 liters of heat.Under 100 ℃ and 5～10 torrs, made product vacuum-drying 48 hours.The output of product is about 138～148g.
Under 40 ℃, 20 ℃ and 0 ℃, carry out the many polystyrene bromination reactions similar, to confirm the relation of its color characteristics and temperature of reaction to general method.Measure color with two kinds of diverse ways.First kind is ASTM D 1544-68 method, is also referred to as to add nail (unit of length) (Gardner) colour code method.Second method is panchromatic poor (Δ E) method, with Hunter (Hunter) L, a, and the b colour code, at the solution of product in chlorobenzene, chlorobenzene concentration is 10% (weight) relatively, calculates according to following formula:
The result is recorded in the Table I.
Table I
Color ℃ adds nail (unit of length) color Δ E to temperature of reaction embodiment sequence number temperature of reaction
1 serial I
a40 3 28.6
2 20 1 16.9
3 0 ＜1 6.9
4 serial II
b40 3 30.0
5 20 1 17.1
6 0 ＜1 8.9
7 serial III
a40 3 30.6
8 20 1 14.9
9 0 ＜1 8.2
A) use Chevron EA3000 polystyrene, 300,000Mw
B) use Polysar HH101-300 polystyrene, 270,000Mw
Just as shown in Table I, under lower temperature, can obtain even more ideal low Δ E data and better add the nail (unit of length) color.
Adopt the polystyrene be used for the recorded low molecular weight of Table I, carry out the serial experiment of another color temperature of reaction.Polystyrene is Hercules Res M1187, and known have a weight-average molecular weight about 900.Outcome record is in Table II.
Table II
Color is to temperature of reaction
Embodiment sequence number bromination temperature ℃ Δ E
1 20 50.2-51.0
2 0 30.2
3 -10 25.5-27.4
In order to confirm the mutual relationship between bromination time and the final product color, with the similar another kind of bromination reaction of general method in, but under 35 ℃, carry out, carry out three experiments with conversion time.Used polystyrene is Chevron EA 3000, and molecular weight is 300, and 000Mw is dissolved in the EDC, forms the solution of about 9.1% (weight), and utilizes butter of antimony to make catalyzer.Measure the product solution total color difference (Δ E) in the chlorobenzene, strength of solution is 10% (weight).The result is recorded in the Table III.
Table III
The color of brominated Polystyrene to embodiment sequence number total bromination time bromination time (hour) bromination temperature ℃ Δ E
1 4 35 20.75
2 7 35 25.15
3 10 35 30.36
Data validation in the Table III 35 ℃ of following bromination times to the mutual relationship between the final product color.In general, color preferably, lower Δ E is the result of shorter bromination time.
In following a series of work, use Chevron AE 3000, molecular weight is 300,000Mw, be dissolved in and become about 10.25% (weight) solution among the EDC, three kinds of different catalyzer that are used for the polystyrene bromination reaction, two kinds of bromizating agents are compared with three kinds of different temperature.The quantity (weight percent) of each catalyzer in polystyrene is 5% in embodiment 1-6; Be 3.88% in embodiment 7-12; Be 4.68% in embodiment 13-18.Measured color characteristics and with the reaction component and response data, be published in the Table IV hereinafter.
Table IV
Color characteristics embodiment sequence number catalyzer bromizating agent bromination temperature ℃ reaction times hour bromination % solid Δ E solution/Δ E 1 SbCl as method variable result
3BrCl 0 5.03 64.51 7.66 2 SbCl
3BrCl 20 5.25 66.59 14.45 3 SbCl
3BrCl 40 4.18 68.74 24.15 4 5bCl
3Br
20 5.00 42.36 11.16 5 SbCl
3Br
220 5.00 42.81 18.02 6 SbCl
3Br
240 5.00 42.39 32.41 7 AlCl
3BrCl 0 3.18 66.99 10.69 8 AlCl
3BrCl 20 3.17 66.62 13.38 9 AlCl
3BrCl 40 3.00 68.56 29.69 10 AlCl
3Br
20 3.48 67.34 22.45 11 AlCl
3Br
220 3.82 67.38 49.29 12 AlCl
3Br
240 3.95 68.03 82.50 13 FeCl
3BrCl 0 3.20 65.46 10.38 14 FeCl
3BrCl 20 3.10 67.09 15.07 15 FeCl
3BrCl 40 3.48 68.40 15.41
a16 FeCl
3Br
20 5.55 66.90 37.14 17 FeCl
3Br
220 4.07 67.81 52.79 18 FeCl
3Br
240 3.67 67.91 70.47
A) the visual aberration of noting, but detecting instrument can not be distinguished
A) the visual aberration of noting, but detecting instrument can not be distinguished
As can be seen by the data in the above-mentioned Table IV, on total meaning, under than the low reaction temperatures scope, use bromine chloride to be bromizating agent, and be catalyzer with butter of antimony, can produce best color.However, the advantage of the inventive method is similarly data proves.For example, consider if under given situation, when effective or required bromizating agent is bromine, by reducing temperature of reaction to 0 ℃ (embodiment 4), then obtain under described two kinds of situations, all making catalyzer with butter of antimony than bromine chloride much better color under 20 ℃ (embodiment 2).As another kind of situation, its temperature of reaction is difficult for reducing, and makes bromizating agent with bromine chloride, and the color of generation is than better with bromine (6 couples of embodiment 3 of embodiment).As another situation,,, still can obtain much better color value (embodiment 13-15) by reducing temperature of reaction and selective chlorination bromine as bromizating agent although can not produce best result as the iron trichloride of catalyzer.In fact, by the Δ E value of comparison solution, people can understand, select iron trichloride, bromine and 0 ℃, can obtain can with butter of antimony, bromine and 40 ℃ of comparable colors, therefore, clearly, can change one or more processing parameters in order to adapt to specific processing parameter.
In the end in Xi Lie the work, compare to confirm temperature of reaction and separation method net effect to color.The separation method of bromination reaction and two kinds of products is following to carry out.Selected polystyrene is DOW XP 6065, and molecular weight is 200,000Mw.All use 4% chlorobenzene solution, produce at Pacific Scientific, light source adding on nail (unit of length) (Gardner) the XL-20 tristimulus colorimeter for " C's ", carries out the mensuration of all colours.
In one 1 liter resin flask, put into 1 of 50.1g polystyrene (counting 0.481 mole) and 600ml with the vinylbenzene repeating unit, 2-ethylene dichloride (EDC), this flask are equipped with distillation tower head (LabGlass LG-1 781 T), spiral cooler and the 500ml jacketed type pressure equilibrium feed hopper of the vertical side arm outlet pipe of heating mantles, mechanical stirrer, thermometer, band of tape-controller.Under agitation solution is heated to and refluxes and remove the EDC/H of 60ml
2O anhydrates so that remove with the form of constant boiling mixture from this system.Solution is chilled to 20 ℃, and adds the solution (0.2g/ml) of 12.5ml butter of antimony in EDC.By 187.5g (1.625 moles) bromine chloride, the bromine chloride solution that the EDC of 2.7g (0.0169 mole) bromine and 187.5g forms was added in 3 hours in the polystyrene solution continuously, kept the bromination temperature simultaneously in 20 ± 2 ℃.This system stir about more than 2 hour typically, be 66% (total bromination time is 5.0 hours) so that the bromine content of final product reaches minimum.
Be no more than the aqueous sodium hydroxide solution of 35 ℃ speed adding 100ml (25% (weight)) with temperature.Stirred the other 10-15 of this mixture minute, and transferred to then in one 2 liters the separating funnel.
Tell organic layer and use twice of the fresh deionized water wash of 700ml.For the second time after the washing, in two the organic phase of 700ml.Product by flashed solvent in boiling water separates
Dilute the organic phase of half with the EDC of 200ml, and put into sizeable feed hopper.This is added in the boiling deionized water that is contained in 1.2 liters of vigorous stirring in 2 liters of Morton resin flask, and described flask is equipped with mechanical stirrer, distillation tower head, condenser, susceptor and heating mantles.Organic solution is being added in the process of boiling water, EDC flashes off with the form of EDC and water mixture, and the slurry that produces is stayed in the flask.
Temperature maintenance is at 91 ℃～100 ℃ in this operating process.After the adding of solution finishes, the gained slurry is incubated 1 hour again under about 100 ℃.
Filter to collect product, on strainer, wash with the deionized water of 2 liters of heat, and then with the deionized water wash of 2 liters of room temperatures.Product is being dried to constant weight under 120 ℃ then in 60 ℃ of following vacuum-dryings (water vent fan) 12 hours in vacuum (5～10 torr).About 65～the 75g of the output of product.Product by precipitation polymers solution in non-solvent separates
Second half EDC dilution of organic phase, and put into sizeable feed hopper with 200ml.This is added in 1.2 liters of methyl alcohol that are placed in 4 liters of Morton resin flask, and this flask is equipped with mechanical stirrer.In 2.5 hours reinforced time, precipitate in room temperature, restir is other 15 minutes subsequently.
Filter and collect product, and in methyl alcohol, remake into slurry, and filter once more and collect with 30 minutes.Product in 60 ℃ of following vacuum-dryings (water vent fan) 12 hours to constant weight.The output of product is about 65～75g.Press ASTM E1313-73 and measure whiteness index (WI) and yellowness index (YI).The result is published in hereinafter the Table V.The calculation formula of WI and YI is as follows:
WI=0.1L (L-5.7b) ... whiteness index (WI) is high more, and then the color of sample is white more.
YI=100 (0.72a+1.79b)/L ... yellowness index (YI) is low more, then the approaching more white of sample.
Table V
Color is to reaction times and separation method embodiment sequence number bromination temperature ℃ WI YI
1 MP
a 20 42.3 15.4
2 W
b 20 37.4 17.2
3 MP 35 12.3 25.6
4 W 35 3.3 28.2
A) MP means sample and precipitates in methyl alcohol.
B) W means sample and separates with boiling water.
The data of Table V clearly illustrate that two kinds of tendencies, and are a kind of, and under the situation that keeps every other variables constant, when carrying out bromination reaction at a lower temperature, the color of brominated Polystyrene is better.Another kind, when brominated Polystyrene separate with the non-solvent precipitator method (methyl alcohol) rather than in boiling water flash distillation desolvate when separating color better (whiter) then.By by the inferred from input data in the last table, can draw similar conclusion.
Therefore clearly, to have in preparation aspect the brominated Polystyrene that improves color characteristics be effectively to method of the present invention.
Based on top disclosed content, the method that adopts the present invention to describe realizes that aforementioned purpose is tangible.Because can understand any change all falls in the present invention for required protection scope significantly, therefore, under the spirit of the present invention that does not depart from and explanation open, can determine specifically to form the selection of main points at this.Especially, needn't be according to the present invention bromizating agent, catalyzer, temperature of reaction and time and other reaction conditionss, be limited on those contents that the application discussed.So scope of the present invention comprises that those fall into whole improvement and change in the appended claims scope.
Claims (17)
1. one kind as giving the additive of polymeric matrix flame retardant resistance and changing the Preparation of Brominated Polystyrene method of color characteristics, it is characterized in that this method may further comprise the steps:
It is 500-1 that preparation has weight-average molecular weight, and 500,000 the solution of polystyrene reactant agent in the halon solvent, this solution contain the described polystyrene reactant agent of 5%～20 weight %;
Add weak Lewis acid bromination catalyst to form solution; The content of catalyzer is 0.2-10 (weight) %;
Add 1～3.3 mole bromizating agent in the described solution by each mole polystyrene repeating unit, described bromizating agent is selected from bromine chloride and bromine;
Reaction is 1-20 hour under-20 ℃～50 ℃ temperature, makes the reaction of described polystyrene and described bromizating agent obtain the reaction product brominated Polystyrene;
The reaction product isolated brominated Polystyrene finally obtains the improved brominated Polystyrene of color characteristics.
2. by the described method of claim 1, wherein said hydrocarbon solvent is selected from tetracol phenixin, chloroform, methylene dichloride, 1,2-ethylene dichloride, vinyl trichloride, sym.-tetrachloroethane, glycol dibromide and composition thereof.
3. by the described method of claim 1, further comprise step with the described reaction of basic metal bisulfite salt brine solution quenching.
4. by the described method of claim 1, wherein said catalyzer is selected from butter of antimony and antimony tribro-and composition thereof.
5. by the described method of claim 4, wherein said separating step carries out in alkane alcohols that can precipitated product or ketone, and comprises the following steps:
Inclusion in the reaction vessel under agitation is added in the alkane alcohols or ketone of energy precipitated product;
Precipitate described brominated polymer; With
Reclaim and dry described brominated polymer.
6. by the described method of claim 5, wherein said ketone is acetone.
7. by the described method of claim 5, wherein said catalyzer is a butter of antimony; Described bromizating agent is a bromine chloride; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
8. by the described method of claim 7, wherein said hydrocarbon solvent is 1, the 2-ethylene dichloride.
9. by the described method of claim 5, wherein said catalyzer is an antimony tribro-; Described bromizating agent is a bromine chloride; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
10. by the described method of claim 5, wherein said catalyzer is a butter of antimony; Described bromizating agent is a bromine; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
11. by the described method of claim 5, wherein said catalyzer is an antimony tribro-; Described bromizating agent is a bromine; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
12. by the described method of claim 4, wherein said separating step is undertaken by flash distillation water, and comprises the following steps:
Under agitation the inclusion of reaction vessel is added in the boiling water and in the preparation slurry, flashes away described solvent and from described slurry, reclaim described brominated polymer.
13. by the described method of claim 12, wherein said catalyzer is a butter of antimony; Described bromizating agent is a bromine chloride; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
14. by the described method of claim 12, wherein said catalyzer is an antimony tribro-; Described bromizating agent is a bromine chloride; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
15. by the described method of claim 12, wherein said catalyzer is a butter of antimony; Described bromizating agent is a bromine; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
16. by the described method of claim 12, wherein said catalyzer is an antimony tribro-; Described bromizating agent is a bromine; It is 5 hours with the described reaction times that described temperature of reaction is 0 ℃.
17. by the described method of claim 1, wherein said polystyrene reactant agent is selected from homopolymerization polystyrene, polystyrene oligopolymer, halogenated polystyrene and alkylation polystyrene.
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| JO3423B1 (en) * | 2008-12-02 | 2019-10-20 | Albemarle Corp | Brominated Flame Retardants And Precursors Therefor |
| CN101701046B (en) * | 2009-10-22 | 2012-04-11 | 国家海洋局天津海水淡化与综合利用研究所 | Preparation method of brominated polystyrene |
| CN101701047B (en) * | 2009-10-22 | 2011-09-07 | 国家海洋局天津海水淡化与综合利用研究所 | Preparation method of spray-dried brominated polystyrene |
| CN105504106A (en) * | 2015-12-24 | 2016-04-20 | 深圳爱易瑞科技有限公司 | Brominated polystyrene with high thermal stability and preparation method of brominated polystyrene |
| CN106565875B (en) * | 2016-11-01 | 2019-07-30 | 珠海澳圣聚合物材料有限公司 | A method of continuously preparing molecular weight-controllable brominated polystyrene master batch |
| CN106565876B (en) * | 2016-11-01 | 2019-03-12 | 珠海澳圣聚合物材料有限公司 | A method of continuously preparing molecular weight-controllable brominated polystyrene |
| CN109867739B (en) * | 2017-12-03 | 2021-07-16 | 潍坊双丰化工有限公司 | Preparation method of brominated polystyrene |
| CN114957517B (en) * | 2022-08-02 | 2022-11-04 | 山东海化集团有限公司 | Method for continuously producing brominated polystyrene |
| CN115636888A (en) * | 2022-12-26 | 2023-01-24 | 山东海化集团有限公司 | Post-treatment method for brominated polystyrene |
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| US4143221A (en) * | 1976-11-11 | 1979-03-06 | Basf Aktiengesellschaft | Manufacture of brominated polymerization products of styrene |
| US4352909A (en) * | 1980-08-20 | 1982-10-05 | Ferro Corporation | Process for the bromination of polystyrenes |
| US5369202A (en) * | 1993-07-22 | 1994-11-29 | Great Lakes Chemical Corporation | Polymers or brominated styrene |
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