CN101490106B

CN101490106B - Process technology for recovering brominated styrenic polymers from reaction mixtures in which they are formed and/or converting such mixtures into pellets or into granules or pastilles

Info

Publication number: CN101490106B
Application number: CN200780027163.7A
Authority: CN
Inventors: 查尔斯·H.·科利赫; 约翰·F.·巴尔霍夫; 道格拉斯·W.·卢瑟; 小罗伯特·C.·赫恩登; 龙尼·W.·利恩; 布鲁斯·C.·彼得斯; 亚瑟·G.·马克; 戴维·A.·李
Original assignee: Albemarle Corp
Current assignee: Albemarle Corp
Priority date: 2006-07-20
Filing date: 2007-07-18
Publication date: 2013-04-17
Anticipated expiration: 2027-07-18
Also published as: CN101490106A; JO3051B1

Abstract

Brominated styrenic polymer is recovered from solution in a vaporizable solvent by converting the solution in a devolatilization extruder into a brominated styrenic polymer melt or flow and a separate vapor phase comprised predominately of vaporizable solvent, recovering the melt or flow from the devolatilization extruder, and allowing or causing the melt or flow to solidify. The solidified brominated styrenic polymer can be subdivided into a powder or pelletized form. Pellets so made have improved hardness and/or crush strength properties along with reduced formation of fines. Brominated anionic styrenic polymer is preferably used in the process.

Description

Be used for from the reaction mixture recovery brominated styrene base polymer that forms the brominated styrene base polymer and/or the processing technology that this mixture is converted into particle or granule or lozenge

Background technology

U.S. Patent number 5,677,390,5,686,538,5,767,203,5,852,131,5,852,132,5,916,978,6,113,381,6,207,765,6,232,393,6,232,408,6,235,831,6,235,844,6,326,439 and 6,521,714 have described the processing technology of wishing very much, for example have the brominated Polystyrene of knowing character of any previously known brominated styrene base polymer for the production of the brominated styrene base polymer.In this connection, refer to the brominated polymer of producing by the multipolymer bromination of the styrenic polymer that is pre-existing in such as polystyrene or vinylbenzene and at least a other vi-ny l aromatic monomers such as used term " brominated styrene base polymer " in this paper specification sheets and in the claim and " brominated Polystyrene ", it is different from oligopolymer or polymkeric substance oligomeric by the monomer of more than one brominated styrenes or that polymerization is produced, and the latter's oligopolymer or the character of polymkeric substance are typically significantly different from brominated Polystyrene in many aspects.In addition, comprise that such as this paper claim is used, the term that the person skilled in the art commonly uses " anionic styrenic polymer " or " anionic polystyrene " expression, described polymkeric substance is by utilizing anionic polymerization initiator such as lithium alkylide to produce.Term " brominated styrene base polymer " and " brominated Polystyrene " comprise and belong to together with term " brominated anionic styrenic polymer " or " brominated anionic polystyrene ".These common names also comprise the brominated styrene base polymer of for example producing by styrenic polymer or the polystyrene bromination of radical polymerization manufacturing.

Shown in above-mentioned patent, the common method that reclaims the brominated styrene base polymer from the bromination reaction mixture liquid phase comprises: make catalyst deactivation with moisture quencher, separate the organic phase that contains brominated polymer from aqueous phase, thereby usually the organic phase of its solvent being sent into boiling water comes this organic phase of stripping to bromizate polymer precipitation, reclaim the brominated polymer of precipitation such as filtration or centrifugation by the liquid-solid separation technology, and the brominated styrene base polymer in small, broken bits that will obtain is dry.If it will be very favorable can finding to reclaim in more efficient and more cheap mode the method for brominated styrene base polymer.

When the brominated styrene base polymer mixes with matrix thermoplastic polymer when fire-retardant, wish that the brominated styrene base polymer is the form of particle or granule or lozenge.Regrettably, the feature of brominated anionic styrenic polymer such as brominated anionic polystyrene is, when attempting product granulation shape, tend to form a large amount of small-particles and powder, and so same in a way by the brominated styrene base polymer of radical polymerization manufacturing.Discovery is during moulding, processing and/or packing, unless bonding by the tackiness agent that adds etc., otherwise particle trend division and revert to small-particle and powder in small, broken bits typically is called as " fine powder ".Because this feature, the granulation of various routines or briquetting step are not suitable for producing the brominated anionic styrenic polymer that is substantially free of fine powder and basically keeps not containing fine powder during shipment and processing.As can easily understanding, existence or formation fine powder are not only unfavorable to the outward appearance of granular product in this series products, and are that the human consumer is undesirable.

Some human consumers think, for particularly the brominated anionic styrenic polymer is effectively as the fire retardant in some thermoplastic polymer with the brominated styrene base polymer, it also is undesirable using tackiness agent or other material that adds to keep the integrity of particulate fire retardant.Thereby hope can be produced particularly brominated anionic styrenic polymer of undoped particulate state brominated styrene base polymer, can not form the fine powder of undesirable amount during their preparation, packing, shipment and processing.

At particulate state brominated styrene base polymer particularly in the production of brominated anionic styrenic polymer, importantly enhance productivity and production cost is minimized.The recovery of fine powder and cycling and reutilization prevent the product waste and need not to consider the refuse processing.Yet the fine powder amount of generation, recovery and cycling and reutilization is larger, and the productivity of particle is lower in the Board Lot polymkeric substance that stands to granulate.Therefore, if can find a kind of method, with expensive-efficiently mode prepare the brominated styrene base polymer particularly undoped brominated anionic styrenic polymer avoid simultaneously forming excessive fine powder so that the productivity of the high-quality particle that do not detract in fact then will be very favorable.In the situation that the brominated anionic styrenic polymer, will be desirable especially if can find to produce the method for polymkeric substance granule or lozenge.This can be in the technique (comprising whole technique) of product, process and store and product is being delivered to the final user and used by the final user in the process of product and obtain many important advantages.

Summary of the invention

Compare with above mentioned recovery method commonly used, according to one group of embodiment of the present invention, can be more prone to and efficiently with lower cost from the solution of solvent, particularly from the solution of the solvent that forms therein them, reclaim particularly brominated anionic styrenic polymer of brominated styrene base polymer.

According to another group embodiment of the present invention, can produce now and pack the undoped granular brominated styrene base polymer, particularly brominated anionic styrenic polymer that are substantially free of fine powder.Comprise in the claim used such as this paper, term " particle ", " granular ", " granulation " if etc. refer to and adopt conventional screening operation screening, size range to be in sieve that can be by about 4 standard U.S. size of mesh and be retained in approximately some particles on the sieve of 40 standard U.S. size of mesh.Particle in such size range can have any shape and therefore also can be known as granule, thereby comprising that such as this paper claim is used, term " particle ", " granular ", " granulation " philosophy comprise " granule ", " granular ", " granulation " etc.Because static charge, incomplete screening etc., the thinner particle of size that some are a small amount of (for example, based on the gross weight of the particle in such size range less than about 5wt%) may be retained in the product.With regard to comprise the used term of claim " undoped " such as this paper with regard to, meaned before the preparation particle or during add extra composition such as tackiness agent (for example, wax or other polymerization or oligomeric), inorganic salt etc. in the brominated styrene base polymer.Otherwise the brominated styrene base polymer only is included in it and prepares the residual impurity that is retained in afterwards in the brominated polymer.

In addition, the preferred embodiment of the invention might avoid forming on thrifty basis the fine powder of undesirable amount, because only produce in operation the fine powder of relatively small amount, and the undoped particle that forms has good hardness and crushing strength.In fact, in the preferred technique of the present invention, the formed a small amount of dried fine powder that may be present in the product can be recovered in operation also recirculation and need not too many expense or difficulty.

Other particularly preferred embodiment of the present invention can be produced the brominated anionic styrenic polymer of granule or lozenge form, and it has relatively level and smooth surface thereby more easily processes, stores, loads and transports and use and can not form the fine powder of undesirable amount.

In each embodiment of the present invention, in the devolatilization forcing machine, form " polymer melt " by the preferred brominated anionic styrenic polymer of brominated styrene base polymer, " polymer fluid ", " melt " or " fluid ", comprise that such as this paper claim is used, the term " polymer " melt "; " polymer fluid "; " melt " or " fluid " refers to that brominated styrene base polymer in the devolatilization forcing machine becomes melt substance and/or the fact of the material that fully softened, and these materials will be by the thrust that is provided by an one above screw rod in this device by the rest part (comprising any increase part that can add to wherein) of (namely flowing through) devolatilization forcing machine and the die head that is arranged in this device discharge end thereafter.Strictly speaking, no matter whether formed the true melt of brominated styrene base polymer or brominated styrene base polymer only softening to as just now as described in the degree that flows all can.

Therefore, in one group of embodiment of the present invention, provide and from the solution of the preferred volatilizable halogenated solvent of volatilizable solvent, reclaimed the technique that typically has at least about the brominated styrene base polymer of 50wt% bromine content.These techniques comprise: will comprise the independently gas phase that the mixture of the viscosity extruded of brominated styrene base polymer and volatilizable organic solvent is converted into brominated styrene base polymer melt or fluid and mainly comprises volatilizable solvent in the devolatilization forcing machine, from the devolatilization forcing machine, reclaim described brominated styrene base polymer melt or the fluid of melt or flow morphology, and allow or make described melt or fluid solidifies.Organize in the preferred embodiment at this, preferably this technique comprises that further the melt that will solidify is further divided into Powdered, granular or particulate state.Substitute or in addition, this technique further comprises and reclaims gas phase and allow or make its liquefaction to be volatilizable solvent.Preferably with the solvent recycled of this liquefaction as the volatilizable solvent that is used to form other brominated styrene base polymer solution.In this group embodiment particularly preferred embodiment, make the mixture less than the brominated styrene base polymer that can extrude viscosity and volatilizable organic solvent be converted into the mixture that can extrude viscosity, in the devolatilization forcing machine, process as described in before such as this section subsequently.This from less than extruding viscosity to the conversion that can extrude viscosity, typically finish by following operation: by for example distillation or flash distillation from less than the preferred volatilizable halogenation organic solvent of the volatilizable organic solvent of removing capacity the mixture that can extrude viscosity to form the mixture that can extrude viscosity.In this group embodiment particularly preferred embodiment, less than the following formation of the mixture that can extrude viscosity: the styrenic polymer of bromination in the preferred halogenation organic solvent of volatilizable organic solvent, and by bromination technique obtain typically by have at least about the brominated styrene base polymer of 50wt% bromine content and the preferred halogenation organic solvent of volatilizable solvent form less than the mixture that can extrude viscosity.Usually this mixture less than extruding viscosity is to have 50wt% at least preferably at least about 60wt% and more preferably at least about the solution of brominated styrene base polymer in the preferred volatilizable halogenation organic solvent of volatilizable organic solvent of 67wt% bromine content.In some embodiments of this group embodiment, cause bromination reaction and/or the method detailed that causes subsequently forming less than the operation that progressively causes of the mixture that can extrude viscosity is used as primary operation.In some embodiments of this group embodiment, as this section before as described in, in the devolatilization forcing machine, process before the mixture of the brominated styrene base polymer can extrude viscosity and volatilizable organic solvent, with this mixture coalescence filtration to remove the water of carrying secretly that may be present in this mixture and the salt of dissolving.Another that can carry out in this organizes each embodiment of embodiment preferably operates and is, if the mixture that can extrude viscosity is being lower than approximately under 175 ℃ the temperature for solid-state, be in previous such as this section as described in the devolatilization forcing machine for the extrudable viscosity of processing before, with this mixture preheating.This preheating can be finished making in preheater section that the devolatilization forcing machine is combined, perhaps by with preheater independently with its suitably the amounts of preheat import that enters the devolatilization forcing machine finish.Preheating should raise the temperature of mixture in order to can it be sent into the devolatilization forcing machine with the state of softening at least movably state, partial liquefaction, liquefaction or with extrudable viscosity.In addition, can pass through the temperature control that screw design, screw speed and/or roller temperature are regulated to be affected in the forcing machine.In addition, the devolatilization forcing machine can have cooling power and avoids local superheating.

In another group embodiment of the present invention, provide origin freely the extrudate preparation of the devolatilization forcing machine of the described running of the preceding paragraph typically have technique at least about the particulate state brominated styrene base polymer of 50wt% bromine content.Each embodiment of this group embodiment is utilized the described any embodiment of processing the mixture that can extrude viscosity that relates in the devolatilization forcing machine of the preceding paragraph, comprises in each embodiments of more than one operations of implementing before the described this processing that relates in the devolatilization forcing machine of the preceding paragraph each.Thereby replace from the devolatilization forcing machine, reclaiming brominated styrene base polymer melt or the fluid of melt or flow morphology and allowing or make described melt or fluid solidifies, make in embodiment from the melt of devolatilization forcing machine or fluid by die head to produce newborn brominated styrene base polymer melt or the bar of fluid in this group, allow or make the above bar of this bar to solidify, and this bar is divided into the brominated styrene base polymer particle of curing again.The preferred method of processing this bar forms the other embodiments of this group embodiment of the present invention.

The present invention also has another group embodiment to relate to the technique of producing undoped brominated anionic styrenic polymer granule or lozenge, and this technique comprises:

In the devolatilization forcing machine, the mixture of brominated styrene base polymer and volatilizable organic solvent is converted into the independently gas phase of melt or fluid and the described solvent of brominated anionic styrenic polymer; And

The piston flow that forms downward orientation from the manifold that approaches cooling plane of motion member or at least one mouth of pipe the ozzle by described melt or fluid; the not saturating cooling fluid of described plane institution movement also has end face and the bottom surface; thereby between the bottom of the mouth of pipe and described end face, a gap is arranged; so that at least a portion melting undoped brominated anionic styrenic polymer piston or (i) the described gap of cross-over connection and form independently single granule or lozenge at the end face of described plane institution movement; perhaps (ii) freely falls and drops on the end face of described plane institution movement from the bottom of the mouth of pipe; and form single granule or lozenge at the end face of described plane institution movement, by cooling fluid mist or the thin described plane institution movement of cooling that drips that contacts described plane institution movement bottom surface.

By description, accompanying drawing and claims subsequently, above and other embodiment of the present invention, feature and/or advantage will become further obviously.

Except relate to by the brominated anionic styrenic polymer for example the brominated anionic polystyrene prepare the embodiment of granule or lozenge; in all other embodiments of the present invention those and those embodiments hereinafter described as mentioned above, preferred brominated styrene base polymer is materials that those styrenic polymer (" free radical styrenic polymer ") brominations that form by radical polymerization form.Particularly preferably be the brominated styrene base polymer by styrenic polymer (" anionic styrenic polymer ") the bromination formation of anionoid polymerization preparation.In the free radical styrenic polymer, the polystyrene that does not contain rubber (" radical polymerization vinylbenzene ") that preferably forms by radical polymerization.In anionic styrenic polymer, the polystyrene that does not contain rubber (" anionic polystyrene ") that preferably forms by anionoid polymerization.Although can use the brominated styrene base polymer of brominated styrene base polymer as being formed by the styrenic polymer bromination that forms by cationoid polymerisation of other type, they are not preferred.

Comprise that such as this paper claim is used, term " can be extruded viscosity " and means mixture and fall to have under second (reciprocal second) approximately 5000 to approximately 5 100 when about 175 ℃ of temperature in about 300 ℃ of scopes, viscosity in 000, the 000 centipoise scope.This mix flow (for example by means of suitable pump) is entered and by the devolatilization forcing machine, and processed in forcing machine, emit the volatilizable organic solvent of gaseous state in mixture is in above-mentioned scope at least and/or when being higher than an above temperature of above-mentioned scope.With regard to term " mixture ", the mixture that means specific components, this mixture can be for solid-state, the perhaps form of preferred at least a liquid phase, and no matter a kind of liquid phase or more than a kind of form of liquid phase it can have suspension more than one solid phases wherein.It should be noted that term " can extrude viscosity " and refer to when mixture is processed the viscosity that obtains in the devolatilization forcing machine.Before the reason, the mixture that can extrude viscosity needn't and not be in usually can extrude viscosity herein.

In all process implementing schemes of the present invention, the mixture that preferably can extrude viscosity is just not solid-state, and is to have the form that solid suspension can be arranged or disperse the thickness flowable mass of liquid phase wherein.

In this manual or in claim subsequently, relate to the pressure (vacuum) of the decline that puts on melt or fluid with all references that devolatilization forcing machine or its are used relevant " pressure ", and to put on the power of melt or fluid irrelevant with an above screw rod of devolatilization forcing machine.In order to determine the organic solvent amount in the polymkeric substance in any embodiment of the present invention, wish to adopt NMR to analyze.The result should be presented at the brominated styrene base polymer melt that leaves the devolatilization outlet of extruder under the quiet rum or fluid and comprise mean number and be less than approximately 10,000ppm (wt/wt), preferably be less than approximately 5000ppm (wt/wt), more preferably less than the about organic solvent of 1000ppm (wt/wt).

Description of drawings

Fig. 1 be explanation for the preparation of with the skeleton diagram of the whole technique of separating the undoped brominated styrene base polymer of particulate state of the present invention.

Fig. 2 is the schematic top view that is suitable for according to the apparatus system of the undoped brominated styrene base polymer of explained hereafter of the present invention particulate state of the present invention and the undoped brominated anionic styrenic polymer of preferred particulates shape.

Fig. 3 is the schematic side elevation of the system of Fig. 2.

Fig. 4 is that explanation is for the preparation of the skeleton diagram of the whole technique of the present invention of undoped brominated styrene base polymer granule or lozenge.

Being described in further detail of invention

Relate to some embodiments that reclaim the brominated styrene base polymer

A) be used for from the mixture of volatilizable organic solvent, reclaiming the technique of brominated styrene base polymer, this technique comprises: process in the devolatilization forcing machine by typically having at least about 50wt% preferably at least about 60wt% and the mixture that can extrude at least viscosity that more preferably forms at least about brominated styrene base polymer and the volatilizable organic solvent of 67wt% bromine content, the gas phase that forms the melt of this brominated styrene base polymer or fluid and formed by volatilizable organic solvent, from the devolatilization forcing machine, reclaim this brominated styrene base polymer melt or the fluid of melt or flow morphology, and allow or make described melt or fluid solidifies.Preferably under devolatilization forcing machine quiet rum, leaving this brominated styrene base polymer melt of devolatilization outlet of extruder part or fluid comprises mean number and is less than approximately 10,000ppm (wt/wt), more preferably less than about 5000ppm (wt/wt), further preferably be less than the approximately organic solvent of 1000ppm (wt/wt).Preferably return the getter phase.

B) be used for from reclaim the technique of brominated styrene base polymer the mixture of volatilizable organic solvent, this technique comprises

The mixture that can extrude viscosity is introduced the inlet part of the devolatilization forcing machine of running continuously, described mixture comprises typically having at least about 50wt% preferably at least about 60wt% and more preferably at least about brominated styrene base polymer and the volatilizable organic solvent of 67wt% bromine content, described forcing machine have inlet part and polymer melt or polymer fluid exit portion and can (a) under the temperature that differs from one another, at least two parts that turn round under the pressure that (b) differs from one another, one of this at least two parts is arranged in another upstream of these at least two parts, and this devolatilization forcing machine has the vapor collection device that is suitable for being collected in the volatile matter that forms in these at least two parts; And

Comparing the described parts that are arranged in the downstream of running under higher temperature and the lower pressure condition with the described temperature and pressure condition that is arranged in the parts of upstream, in order to (a) in the devolatilization forcing machine, form fluid or the melt of described polymkeric substance, and emit from the outlet of polymer melt or polymer fluid, and the volatile matter of the solvent composition of (b) mainly being emitted by the polymkeric substance in described at least two parts can be collected by described vapor collection device, under devolatilization forcing machine quiet rum, leaving the melt of this brominated styrene base polymer of devolatilization outlet of extruder or fluid comprises mean number and is less than approximately 10,000ppm (wt/wt), preferably be less than approximately 5000ppm (wt/wt), more preferably less than the about organic solvent of 1000ppm (wt/wt).

C) be used for from the technique of the mixture recovery brominated styrene base polymer with the preferred volatilizable halogenated solvent of volatilizable solvent, this mixture is less than the mixture that can extrude viscosity, for example be included in approximately 15 in the about 40wt% scope pass through bromination to about 50wt% be approximately 2000 to arrive approximately 200 at least about 60wt% and the brominated anionic styrenic polymer (preferred brominated anionic polystyrene) that more preferably forms at least about the bromine content of 67wt% and GPC weight-average molecular weight preferably, in 000 scope, preferred approximately 2000 to approximately 10, in 000 scope, 3000 solution of anionic styrenic polymer preferred anionic polystyrene in about 7000 scopes more preferably from about, this technique comprises:

By distillation, preferably by flash distillation this mixture is concentrated or is converted into the mixture that can extrude viscosity; And

With this mixture of extruding viscosity as above embodiment A) or embodiment B) charging in the described technique.

Relating to by utilizing distillation or flash concentration or transforming that for example solution or suspension obtain several advantages to reach concentrated or to be converted in embodiment of the present invention of the mixture that can extrude viscosity less than the precursor mixture that can extrude viscosity.Except mixture that will be denseer or solution are introduced the devolatilization forcing machine for being converted into melt or polymer fluid, thereby reduce the running recovered solvent amount by the devolatilization forcing machine, the initial soln of brominated styrene base polymer is heated to realize distillation or flash distillation.Thereby by promptly distilling or the mixture of the viscosity extruded of flash distillation is sent into the devolatilization forcing machine, this mixture of preheating is converted into melt or the required total heat energy of polymer fluid thereby reduce the devolatilization forcing machine with mixture effectively.Concentrated also the solvent of water and distillation is together removed, so that any organic solvent of removing in the devolatilization forcing machine is anhydrous and is suitable for directly being recycled to bromination and less than drying step independently.In addition, this anhydrous charging corrodibility of delivering to the devolatilization forcing machine is less, because do not have water in this charging.Need not concentrate in the embodiment of brominated styrene base polymer mixture, by before delivering to the devolatilization forcing machine at the mixture that can extrude viscosity its preheating being obtained same advantage (except except anhydrating).

In addition, do not resemble U.S. Patent number 5,043,421 recovery arts demand adopts at least a non-solvent such as alkanol or ketone (particularly methyl alcohol, 2-propyl alcohol or acetone) in forcing machine, recovery embodiment of the present invention does not need to adopt any this non-solvent.In other words, recovery optimal process of the present invention is not sent any this non-solvent into the devolatilization forcing machine, but and the preferred extrudate that reclaims do not have this alcohol or the ketone non-solvent of detection limit.

Relate to some embodiments that form particulate state brominated styrene base polymer

1) is used for by the technique at the mixture production particulate state brominated styrene base polymer of volatilizable organic solvent, this technique comprises: process in the devolatilization forcing machine by typically having at least about 50wt% preferably at least about 60wt% and the mixture that can extrude at least viscosity that more preferably forms at least about brominated styrene base polymer and the volatilizable organic solvent of 67wt% bromine content, the gas phase that forms the melt of this brominated styrene base polymer or fluid and formed by volatilizable organic solvent, from the devolatilization forcing machine, reclaim this brominated styrene base polymer melt or the fluid of melt or flow morphology, and this melt or fluid are converted into the solid granulates of brominated styrene base polymer.

2) be used for technique by the solution production particulate state brominated styrene base polymer of volatilizable organic solvent, this technique comprises: will typically have at least about 50wt% in the devolatilization forcing machine, preferably at least about 60wt%, more preferably be converted into brominated styrene base polymer melt or fluid and the main gas phase that is formed by volatilizable organic solvent at least about the brominated styrene base polymer of 67wt% bromine content and the mixture of volatilizable organic solvent, allow or make the described melt of brominated styrene base polymer of melt or flow morphology or fluid by the devolatilization forcing machine die head of flowing through, thereby produce brominated styrene base polymer melt or fluid new life's bar, allow or make described bar to solidify, and bar is further divided into the brominated styrene base polymer particle of curing.

3) be used for by the technique at the solution production particulate state brominated styrene base polymer of volatilizable organic solvent, this technique comprises:

In the devolatilization forcing machine, with the mixture of brominated styrene base polymer and volatilizable organic solvent, the mixture of preferred brominated anionic styrenic polymer and volatilizable organic solvent is converted into the independently gas phase of melt or fluid and the described solvent of the preferred brominated anionic styrenic polymer of brominated styrene base polymer;

To extrude from the melt of devolatilization forcing machine or polymer fluid the bar of the movement of the polymer melt extruded with generation by die head or polymer fluid;

Allow and/or make the bar of this movement to solidify and broken, divide again or otherwise be converted into brominated styrene base polymer particle; And

Make particle grade into uniform size from this product, to remove and reclaim (a) if any, excessive particle, and (b) if any, may be present in the fine powder in this product.

Can and preferably as the said products reclaims embodiment, implement the first step that this embodiment is mentioned, in the devolatilization forcing machine, brominated styrene base polymer solution is converted into melt or the polymer fluid of brominated styrene base polymer.In addition, by before denseer solution is delivered to the devolatilization forcing machine, utilizing this solution of flash distillation preheating or enriched material, can obtain to reduce quantity of solvent to be removed and reduce devolatilization forcing machine production polymer melt or the above-mentioned advantage of the heat energy that polymer fluid is required.

Except the advantage that provides by pre-concentration and/or preheating brominated styrene base polymer solution, the advantage of the above-mentioned granulation embodiment of the present invention is: can adopt for example undoped brominated anionic styrenic polymer of undoped brominated styrene base polymer, thereby and form for example particle of undoped brominated anionic styrenic polymer of undoped brominated styrene base polymer, its tool character likely is such as the hardness that improves and be reduced in manufacturings, processings, store and application during the tendency of generation fine powder.

4) for the preparation of the technique of particulate state brominated styrene base polymer, this technique comprises:

In volatilizable organic solvent and in the presence of the Lewis acid bromination catalyst, in airtight reactive system under super-atmospheric pressure with the styrenic polymer bromination, in this reactive system basically all hydrogen halide byproducts be retained in the reaction mixture;

Thereby the catalyzer cancellation is formed the organic phase and the water that (ii) comprises hydrogen halide that (i) comprises the brominated styrene base polymer of dissolving;

With phase (i) and (ii) separated from one another, and if phase (i) have less than the viscosity that can extrude viscosity, the organic phase of (i) is concentrated to form the mixture that can extrude viscosity;

The mixture that the organic phase of (i) maybe can be extruded viscosity is introduced the liquid-inlet part of the devolatilization forcing machine of running continuously, this forcing machine have liquid-inlet part and polymer melt or polymer fluid exit portion and can (a) under the temperature that differs from one another, at least two parts that (b) under the pressure that differs from one another, turn round, one of this at least two parts is arranged in another upstream of these at least two parts, and this devolatilization forcing machine has the vapor collection device that is suitable for being collected in the volatile matter that forms in these at least two parts; And

Comparing the described parts that are arranged in the downstream of running under higher temperature and the lower pressure condition with the described temperature and pressure condition that is arranged in the parts of upstream, in order to (a) in the devolatilization forcing machine, form flowable polymer melt or the polymer fluid of described polymkeric substance, and can leave from the outlet of at least one polymer melt or polymer fluid, and the volatile matter of the solvent composition of (b) mainly being emitted by the polymkeric substance in described at least two parts is collected by described vapor collection device;

Make the continuous bar of the movement of polymer melt that the described polymer melt that leaves the devolatilization forcing machine or polymer fluid extrude with generation by die head or polymer fluid;

Allow and/or make the bar of this continuous moving to solidify and broken, divide again or otherwise be converted into brominated styrene base polymer particle.

Further embodiments more of the present invention for the production of granular product

Of the present invention also have other embodiment to relate to:

The undoped brominated styrene base polymer of new particulate state, preferred new undoped particulate state brominated anionic styrenic polymer, it has outstanding hardness and/or crushing strength character;

For the production of high-purity melt of brominated anionic styrenic polymer (particularly brominated anionic polystyrene) or the new continuous processing of fluid, it adopts (1) anionic styrenic polymer (particularly anionic polystyrene), (2) bromizating agent (particularly bromine), (3) lewis acid catalyst (particularly wherein halogen atom be bromine and or the aluminum halide catalyst of chlorine, and (4) volatilizable organic solvent (particularly volatilizable halogenated solvent) is as raw material;

New continuous processing for the production of the high purity granular of brominated anionic styrenic polymer (particularly brominated anionic polystyrene), it adopts (1) anionic styrenic polymer (particularly anionic polystyrene), (2) bromizating agent (particularly bromine), (3) lewis acid catalyst (particularly wherein halogen atom be bromine and or the aluminum halide catalyst of chlorine, and (4) volatilizable organic solvent (particularly volatilizable halogenated solvent) is as raw material;

New particulate state brominated anionic styrenic polymer (particularly new undoped particulate state brominated anionic styrenic polymer), it has ion bromine (the being bromide) content of reduction amount, and outstanding hardness and/or crushing strength character.

In each embodiment of the present invention, under quiet rum, typically have mean number from the extrudate of devolatilization forcing machine and be less than approximately 10,000ppm (wt/wt), preferably be less than approximately 5000ppm (wt/wt), more preferably less than the about organic solvent of 1000ppm (wt/wt), thereby tool hardness likely and intensive property form the reduction in propensity of fine powder simultaneously.

Relate to some embodiments that form brominated styrene base polymer granule or lozenge

These embodiments comprise the technique of producing undoped brominated anionic styrenic polymer granule or lozenge, and this technique comprises:

In this technique, the endless belt that preferred mobile plane institution movement is not saturating cooling fluid is ring steel belt for example.On-stream; the undoped brominated anionic styrenic polymer of at least a portion melting described gap of piston cross-over connection also forms independently single granule or lozenge at the end face of described plane institution movement; perhaps the undoped brominated anionic styrenic polymer of this melting of at least a portion piston freely falls and drops on the end face of plane institution movement from the bottom of the mouth of pipe, and forms single granule or lozenge at the end face of plane institution movement.So running is so that (a) the described gap of the undoped brominated anionic styrenic polymer of at least a portion melting piston cross-over connection and form independently single granule or lozenge at the end face of described plane institution movement; Perhaps wherein the undoped brominated anionic styrenic polymer of the described melting of (b) at least a portion piston freely falls and drops on the end face of described plane institution movement from the bottom of the mouth of pipe, and forms single granule or lozenge at the end face of described plane institution movement; (a) and (b) with alternately or random mode occur.

Although can use other cooling fluid, the mist of described cooling fluid or thin dripping are preferably cooled off water smoke or thin dripping.Preferably with mist or the thin bottom surface that is applied to described plane institution movement of dripping, it is lower than the zone that end face at described plane institution movement forms single granule independently or lozenge.

Another embodiment of the invention is the whole technique for the production of the brominated anionic styrenic polymer of undoped brominated anionic styrenic polymer granule or lozenge form.This technique comprises:

In volatilizable organic solvent and in the presence of the Lewis acid bromination catalyst, in airtight reactive system under super-atmospheric pressure with the anionic styrenic polymer bromination, in this reactive system basically all hydrogen halide byproducts be retained in the reaction mixture;

The piston flow that forms downward orientation from the manifold that approaches cooling plane of motion member or at least one mouth of pipe the ozzle by described flowable polymer melt or fluid; the not saturating cooling fluid of described plane institution movement also has end face and the bottom surface; thereby between the bottom of the mouth of pipe and described end face, a gap is arranged; so that at least a portion melting undoped brominated anionic styrenic polymer piston or (i) the described gap of cross-over connection and form independently single granule or lozenge at the end face of described plane institution movement; perhaps (ii) freely falls and drops on the end face of described plane institution movement from the bottom of the mouth of pipe; and forming single granule or lozenge at the end face of described plane institution movement, the cooling fluid mist or carefully drip of described mobile member by contacting described plane institution movement bottom surface is cooled.

In this embodiment, preferred mobile plane institution movement is the saturating endless belt of cooling fluid not, and is more preferably ring steel belt.In addition, the mist of cooling fluid or thin dripping are preferably cooled off water smoke or thin dripping.Preferably with mist or the thin bottom surface that is applied to described plane institution movement of dripping, it is lower than the zone that end face at described plane institution movement forms single granule independently or lozenge.

The brominated styrene base polymer

Formed according to the present invention by bromination and to be recovered and/or the styrenic polymer of the brominated styrene base polymer of granulating is homopolymer and/or multipolymer more than more than one of more than one above vi-ny l aromatic monomers.The preferred vinyl aromatic monomer has formula:

H ₂C＝CR-Ar

Wherein R is the alkyl group of hydrogen atom or carbonatoms 1 to 4, and Ar is the aromatic yl group (comprising the cyclosubstituted aromatic yl group of alkyl) of carbonatoms 6 to 10.The example of this monomer is vinylbenzene, alpha-methyl styrene, o-methyl styrene, a vinyl toluene, p-methylstyrene, to ethyl styrene, isopropenyl toluene, vinyl naphthalene, pseudoallyl naphthalene, vinyl biphenyl, vinyl anthracene, dimethyl styrene and t-butyl styrene.Polystyrene is preferred reactant.When making the brominated styrene base polymer by the multipolymer bromination of two or more vi-ny l aromatic monomers, optimization styrene is a kind of in the monomer, but and this vinylbenzene comprises at least 50 % by weight and preferably at least about the copolymerizable vinyl groups aromatic monomer of 80 % by weight.Term " aromatic vinyl " and " cinnamic " that interchangeably use of this paper is relevant with monomer or polymkeric substance.

The aromatics side group composition for the treatment of the brominated styrene base polymer can be replaced by alkyl or be replaced by bromine or chlorine atom, but preferably can not replaced like this.Typically, for the production of the GPC weight-average molecular weight (Mw) of the anionic styrenic polymer of brominated anionic styrenic polymer used in the present invention practice approximately 2000 to approximately 200, in 000 scope, preferably approximately 3000 to approximately 10, in 000 the scope, more preferably approximately 3000 in about 7000 scope.The polymolecularity of this anionic styrenic polymer is typically 1 with approximately in the scope between 4, more preferably 1 with approximately in the scope between 2.Typically, adopt the GPC weight-average molecular weight (Mw) of technique of the present invention by the styrenic polymer produced for the production of the radical polymerization of brominated styrene base polymer approximately 30,000 to approximately 500, in 000 scope, preferably approximately 50,000 to approximately 300, in 000 the scope, more preferably approximately 150,000 in about 250,000 scope.The polymolecularity of this styrenic polymer of producing by radical polymerization is typically 1 with approximately in the scope between 10.All above-mentioned Mw and polymolecularity numerical value are based on gel permeation chromatography (GPC) technology of describing hereinafter.

Being converted into undoped granular polymkeric substance according to the present invention is single brominated styrene base polymer or the mixture of two or more brominated styrene base polymers, the preferably mixture of single brominated anionic styrenic polymer or two or more brominated anionic styrenic polymers.Said mixture can only contain the bromination homopolymer, only contain bromination multipolymer, perhaps at least a bromination homopolymer and at least a brominated copolymer of styrene monomer.Although can easily produce the lower styrenic polymer of bromine content by the present invention, wish that the bromine content of all these polymkeric substance is at least about 50wt%.The polymkeric substance of preferred these types has the bromine content at least about 60wt%, more preferably at least about 64wt%, and more preferably at least about 67wt%, and even more preferably at least about 68wt%.Common maximum bromine content is about 71wt%, and the polymkeric substance of the 70wt% bromine of having an appointment at most is preferred.Between homopolymer and multipolymer, the brominated Polystyrene polymkeric substance by the radical polymerization manufacturing is preferred, and more preferably brominated anionic poly styrene polymer.

The method of producing styrenic polymer by free radical polymerization process is well known in the art and is in the news in the literature.Referring to for example Encyclopedia of Polymer Science and Engineering, volume 16, John Wiley and Sons, 1989,46-62 page or leaf.For simplicity, no matter odd number or plural number are used for the term " styrenic polymer that free radical is produced " of claim or " polystyrene that free radical is produced " and are illustrated in before the bromination styrenic polymer or polystyrene by adopting or producing in advance by another kind of employing free radical polymerization process.The method for preparing anionic styrenic polymer such as anionic polystyrene also is known in this area and is in the news in the literature.Referring to for example U.S. Patent number 3,812,088; 4,200,713; 4,442,273; 4,883,846; 5,391,655; 5,717,040; With 5,902,865, incorporate its disclosed content into this paper by reference.In the U.S. Patent number of owning together 6,657,028 that is filed on December 2nd, 2003, describe particularly preferred method, incorporated the disclosure of the method into this paper by reference.

In U.S. Patent number 5,677,390; 5,686,538; 5,767,203; 5,852,13 1; 5,852,132; 5,916,978; 6,133,381; 6,207,765; 6,232,393; 6,232,408; 6,235,831; 6,235,844; Disclose the bromination technique that can be used for producing the brominated anionic styrenic polymer in 6,326,439 and 6,521,714, incorporated its disclosed content into this paper by reference.

In all embodiments of the present invention, the brominated styrene base polymer that is preferably formed and/or uses is the brominated anionic styrenic polymer, and in the brominated anionic styrenic polymer brominated anionic polystyrene particularly preferably.

For the preparation of particle of the present invention commercially the typical properties of the brominated Polystyrene of obtainable hope (used polystyrene is by radical polymerization production) comprise following:

Pale powder or the granule of outward appearance/form-form by powder compression

Bromine content-68.5wt%

Tg(℃)-182

Proportion (23 ℃ of@)-2.15

(TA instrument models 2950 (TA instruments model 2950), 10 ℃/min. is at N for TGA ₂Lower):

1% weightlessness, ℃-346

5% weightlessness, ℃-375

10% weightlessness, ℃-383

50% weightlessness, ℃-399

90% weightlessness, ℃-435

This brominated Polystyrene at present can be from Albemarle Corporation (Albemarle Corporation) with title

The HP-7010P fire retardant obtains.The powder compression granular form of this brominated Polystyrene at present can be from Albemarle Corporation with title

The HP-7010G fire retardant obtains.

The typical properties that is preferred for preparing the brominated anionic polystyrene of particle of the present invention comprises following:

The white powder that melt extrudes formation or the particle of outward appearance/form-by powder

Bromine content-67 is to 71wt%

Melt flow index (220 ℃, 2.16kg)-4 to 35g/10min

Tg(℃)-170

Proportion (@23C)-2.2

1% weightlessness, ℃-361

5% weightlessness, ℃-386

10% weightlessness, ℃-394

50% weightlessness, ℃-417

90% weightlessness, ℃-435

At U.S. Patent number 6,521, the method for the preparation of the brominated Polystyrene with above-mentioned character has been described in 714.The brominated anionic polystyrene of granule form at present can be from Albemarle Corporation with title

HP 3010G fire retardant obtains.This granule forms by melt extruding of powder can't help technique preparation of the present invention.

HP 3010P fire retardant is the brominated anionic polystyrene of the powder morphology of Albemarle Corporation's production.

Solvent

The solvent that is present in the brominated styrene base polymer solution that uses in a plurality of embodiments of the present invention can be any liquid solvent, it can gasify being lower than dissolving brominated styrene base polymer wherein and beginning under the temperature of thermal destruction, and with dissolving brominated styrene base polymer wherein disadvantageous reaction does not occur.Typically solvent is comprised of more than one halogenated solvents that have the boiling temperature that is lower than approximately 150 ℃ under the normal atmosphere.Typical halogenated solvent is, wherein each halogen atom is bromine atoms or chlorine atom, and perhaps wherein this solvent comprises the halogenated solvent of at least one bromine atoms and at least one chlorine atom.Less preferred is the solvent that comprises more than one halogen atoms except bromine atoms and/or chlorine atom.The invention is characterized in that solvent can be the solvent that is wherein formed the brominated styrene base polymer in the presence of lewis acid catalyst by the bromination of styrenic polymer.In the patent that the beginning of this specification sheets is quoted, set forth the example of the explanation of these techniques.If yet wish, any suitable stage can be with solvent exchange step with the initial solvent of different volatilizable solvent replacing before sending into the devolatilization forcing machine.Term " volatilizable " only refers to that solvent seethes with excitement being lower than dissolving specific brominated styrene base polymer wherein and beginning to stand under the temperature of thermal destruction that can not receiving amount.This temperature naturally changes as the case may be, and it depends on that factor for example is present in brominated styrene base polymer type in the solvent, time length that solution is in the threshold decomposition temperature and the final used quality control standard of brominated styrene base polymer product.The non-limitative example of suitable organic solvent comprises methylene dichloride, methylene bromide, bromochloromethane, trichlorobromomethane, chloroform, tetracol phenixin, 1,2-ethylene dibromide, 1,1-ethylene dibromide, 1-bromo-2-monochloroethane, 1,2-ethylene dichloride, 1,2-dibromopropane, 1-bromo-3-chloropropane, 1-n-butyl bromide, 2-n-butyl bromide, 2-bromo-2-methylpropane, 1-bromo pentane silane, 1-bromo-2-methylbutane, hexyl bromide 1 bromohexane, 1-heptyl bromide, bromocyclohexane and liquid isomer, homologue or analogue thereof.Can adopt the liquid mixture of two or more such compounds.Bromochloromethane is particularly preferred solvent.If the employing solvent exchange step can be replaced this halogenated solvent with for example volatilizable liquid aromatic solvent.

Dry and concentrated initial solvent solution

Relating to for reclaiming as melt or fluid for the embodiment of the present invention of the technique of subsequently brominated styrene base polymer and relating to for the embodiment of the present invention with the technique of brominated styrene base polymer (solution comprises some water) granulation, hope is by removing basically all water, if not remove most of water, with this solution " drying ".For example, when the Louis acid catalysis bromination forms reaction mixture in suitable organic solvent such as halohydrocarbon or halocarbon solvent by styrenic polymer, typically by with moisture cancellation liquid for example the independent shrend reaction mixture that goes out make catalyst deactivation.Be separated with after the organic phase and aqueous phase separation with the brominated styrene base polymer in the organic solvent, typically some water are retained in this organic phase.In order to remove such water, preferably make " wetting " organic phase (water that namely comprises some residual contentes of following the brominated styrene base polymer for example approximately the organic phase of 1500ppm water) separate most of at least free-water by coalescer, for example reach the level of about 300ppm or water still less).If comprising, the brominated styrene base polymer solution in " drying " organic solvent of gained is less than the approximately brominated styrene base polymer of 40wt%, preferably make this solution stand distillation, more preferably flash distillation is removed with the water that polymers soln keeps organic solvent as collectable gas phase.Form like this denseer basically anhydrous organic solution comprise at least about 50wt% brominated styrene base polymer.The solution of this greater concn ideally is suitable for use as the charging of devolatilization forcing machine.

The technology that is used for coalescence filtration that comprises the coalescence filtration of Separation of Water from the organic liquid system is well-known, and is in the news in the literature, is used for can obtaining from a lot of goods providers from the system of organic liquid system Separation of Water.Be used for realizing that the suitable filtration medium of this separation comprises glass fibre, pottery and sand.The use casting bed is the preferable medium for the embodiment of the present invention that adopts coalescence filtration.

From solvent recuperation brominated styrene base polymer

Reclaiming the of the present invention various techniques of brominated styrene base polymer for the solution from organic solvent, some of them technique is described in the above, and the product that reclaims from the devolatilization forcing machine at first is the melt form or is soft flowable form at least.Can make melt cooling or be cooled off then to transform (for example passing through molding) for for the different shape or the structure that store and load and transport, perhaps can be crushed into little granular or finely powdered.For polymer melt or polymer fluid are converted into particulate state, particularly preferably adopt the process implementing scheme of the present invention of being devoted to prepare granular brominated styrene base polymer.Yet if wish, can adopt at the granulating process described in the disclosed PCT patent application WO 2005/118245 that owns together, the particle of being made by dry powder brominated styrene base polymer by this technique has good quality.Yet, according to obtainable test-results, made in accordance with the present invention particle in addition than produce according to WO 2005/118245 those are better, especially aspect hardness and/or high crush strength.

Reclaim the brominated styrene base polymer by embodiment of the present invention from solution and relate to for example suitable mode as herein described devolatilization forcing machine of selecting and turn round, so as in forcing machine with the solvent gasification, and can and preferably from forcing machine, collect solvent.Preferably adopt lewis acid catalyst with styrenic polymer bromination technique by being recycled to, again utilize recovered solvent.A kind of technique is provided in particularly preferred embodiment of the present invention, it is included in the bromination of implementing styrenic polymer in the liquid reaction mixture in the airtight reactive system under super-atmospheric pressure, so that gas hydrogen halide (HX, bromine or chlorine atom at this X) byproduct do not emit from described airtight reactive system separately and away from this reaction mixture, until in moisture quencher the reaction mixture cancellation is made reaction terminating, quencher destroys catalyzer and dissolves HX and forms Hydrogen bromide or hydrochloric acid (if BrCl is used as bromizating agent).By phase separation step such as sedimentation with discharge lower mutually or the phase above siphon off, the organic phase that will comprise the brominated styrene base polymer is separated from one another with the water that comprises HX.Preferably carry out other washing, any inorganic salt of removing more up hill and dale residual HX and may existing.If wish, can be with the organic phase coalescence filtration, realize from organic phase basically fully water phase separated.Comprise the organic phase of brominated styrene base polymer concentrated after, so the organic phase that this is denseer is introduced the devolatilization forcing machine, wherein with solvent gasification and recovery, emit out basically melt or the polymer fluid of solvent-free brominated styrene base polymer from forcing machine.If aqueous phase HX is HBr, preferably thereafter by (i) thus the stripping water is suitable for the Hydrogen bromide product using or sell so that residual organic solvent and providing to be provided from aqueous phase, (ii) HBr with aqueous phase is converted into elemental bromine, perhaps (iii) makes HBr and moisture metal base reaction production be suitable for the metal bromide salts solution of using or selling, thereby has bromine to be worth (bromine values) from the aqueous phase recovery.

Thereby be provided for preparing the technique of the brominated styrene base polymer of melt or polymer flow volume morphing according to another embodiment of the invention, this polymkeric substance typically has the bromine content at least about 50wt%, preferably at least about 60wt%, more preferably at least about 67wt%, this technique comprises:

If wish, adopt coalescence filtration with phase (i) and (ii) separated from one another to basically being separated fully, if and phase (i) has less than the viscosity that can extrude viscosity, the organic phase of (i) is concentrated to form the mixture that can extrude viscosity, preferably this concentrated by using distillation or flash distillation to finish;

The organic phase of (i) is introduced continuously the liquid-inlet part of the devolatilization forcing machine of running, this forcing machine have liquid-inlet part and polymer melt or polymer fluid exit portion and can (a) under the temperature that differs from one another, at least two parts that (b) under the pressure that differs from one another, turn round, one of this at least two parts is arranged in another upstream of these at least two parts, and this devolatilization forcing machine has the vapor collection device that is suitable for being collected in the volatile matter that forms in these at least two parts; And

Comparing the described parts that are arranged in the downstream of running under higher temperature and the lower pressure condition with the described temperature and pressure condition that is arranged in the parts of upstream, in order to (a) in the devolatilization forcing machine, form flowable polymer melt or the polymer fluid of described polymkeric substance, and emit from the outlet of at least one polymer melt or polymer fluid, and the volatile matter of the solvent composition of (b) mainly being emitted by the polymkeric substance in described at least two parts can and preferably be collected by described vapor collection device, during quiet rum, leaving the polymer melt of this brominated styrene base polymer of devolatilization outlet of extruder or polymer fluid comprises mean number and is less than approximately 10,000ppm (wt/wt), preferably be less than approximately 5000ppm (wt/wt), more preferably less than the about organic solvent of 1000ppm (wt/wt).

Cancellation in the above-mentioned embodiment can be implemented or more preferably independently implement in the container in the reactor that just prepares a collection of brominated styrene base polymer.When implementing bromination on continuous basis, under pressure, the bromination reaction product sent into continuously independently container or zone and in this container or zone, contact with moisture quencher preferably water.During cancellation, catalyst residue tends to collect water, and all hydrogen halide are absorbed in the water basically.State on the implementation (i) in the embodiment and (ii) between be separated after and before introducing devolatilization forcing machine liquid-inlet part, the organic phase that preferably makes (i) through coalescence filtration in order to from the organic phase of brominated styrene-containing base polymer, remove the water entrainment (entrained water) that comprises more than one soluble salts.

The production of particle

Relate in a plurality of embodiments of the present invention for the technique from the mixture production particulate state brominated styrene base polymer of brominated styrene base polymer and volatilizable solvent, this technique comprises:

Randomly form the mixture that to extrude viscosity by what have 40wt% or brominated styrene base polymer content still less than lean mixture, it comprises brominated styrene base polymer and the preferred volatilizable halogenation organic solvent of volatilizable organic solvent, volatilizable organic solvent preferably by styrenic polymer in the presence of lewis acid catalyst therein bromination form the halogenated solvent of brominated styrene base polymer;

To comprise that the mixture of the viscosity extruded of brominated styrene base polymer and volatilizable organic solvent introduces the liquid-inlet part of the devolatilization forcing machine of running continuously, this forcing machine have liquid-inlet part and polymer melt or polymer fluid exit portion and can (a) under the temperature that differs from one another, at least two parts that (b) under the pressure that differs from one another, turn round, one of this at least two parts is arranged in another upstream of these at least two parts, and this devolatilization forcing machine has the vapor collection device that is suitable for being collected in the volatile matter that forms in these at least two parts; And

Comparing the described parts that are arranged in the downstream of running under higher temperature and the lower pressure condition with the described temperature and pressure condition that is arranged in the parts of upstream, in order to (a) in the devolatilization forcing machine, form flowable polymer melt or the polymer fluid of described polymkeric substance, and emit from least one polymer melt or polymer fluid outlet forcibly, and the volatile matter of the solvent composition of (b) mainly being emitted by the polymkeric substance in described at least two parts can and preferably be collected by described vapor collection device, under quiet rum, leaving the polymer melt of this brominated styrene base polymer of devolatilization outlet of extruder or polymer fluid comprises mean number and is less than approximately 10,000ppm (wt/wt), preferably be less than approximately 5000ppm (wt/wt), more preferably less than the about organic solvent of 1000ppm (wt/wt);

Make the bar of the movement of the polymer melt extruded with generation by die head from the melt of devolatilization forcing machine or polymer fluid or polymer fluid;

Allow or make the bar of this movement (for example to solidify, by allowing or the temperature of this bar that moves fully being reduced) and broken, divide again or (for example otherwise be converted into brominated styrene base polymer particle, by reaching ambient air above the extraction bar on the net downwards at travelling belt or the vacuum system that provides off the net, and by jet water course being applied to downwards just on travelling belt or online mobile bar, apply enough power and make at least part of breakage of bar, the porousness of this band or net makes water be passed through net downwards, but the hole is enough carefully with fragmentation, divide again or become granular polymkeric substance strip thing to be retained in this band or online, and allow and/or make fragmentation, divide again or become granular polymkeric substance strip thing from this band or fall into particle sizer on the net, thereby the impact that falls generation may cause bar to produce some other breakages);

Make particle grade into uniform size (for example by utilizing suitable triage techniques) from this product, removing and to reclaim (a) if any, excessive particle, and (b) if any, may be present in the fine powder in this product.

In above-mentioned technique, the preferred fine powder of collecting excessive particle and may being produced by the size classification, and their recirculation entered for example liquid-inlet part of devolatilization forcing machine, any other suitable import to this forcing machine upstream portion, perhaps in the polymer melt that enters die head or polymer fluid, so that particle and fine powder become the part of polymer melt or polymer fluid.When adopting the above first step of choosing wantonly, thereby preferably make rarer solution form the denseer solution of wishing through flash distillation, and will be used for by the halogenated solvent recirculation conduct that the vapor collection device of devolatilization forcing machine is collected at least a portion of styrenic polymer bromination solvent subsequently.

It is technique for the production of particulate state brominated styrene base polymer that the present invention also has another embodiment, and this technique comprises:

To comprise the solution at least about 50wt% brominated styrene base polymer that is dissolved in the volatilizable solvent and send into the devolatilization forcing machine, transformation and this forcing machine that turns round are with the volatilizable solvent of separation from described polymkeric substance, and formation is as polymer melt or the polymer fluid of the described polymkeric substance of extrudate;

Thereby make this extrudate form the bar of the movement of the preferred undoped anionic styrenic polymer of the undoped brominated styrene base polymer of melting by die head; And

By allowing or make the bar in this movement (for example to solidify, by allowing or the temperature of this bar that moves fully being reduced) and broken, divide again or otherwise be converted into brominated styrene base polymer particle, this bar (is for example granulated, by reaching ambient air above the extraction bar on the net downwards at travelling belt or the vacuum system that provides off the net, and by jet water course being applied to downwards just on travelling belt or online mobile bar, apply enough power and make at least part of breakage of bar, the porousness of this band or net makes water be passed through net downwards, but the hole is enough carefully with fragmentation, divide again or become granular polymkeric substance strip thing to be retained in this band or online, and make fragmentation, divide or become granular polymkeric substance strip thing from this band or fall into particle sizer on the net, the impact that falls generation may cause bar to produce some other breakages); And

Make particle size classification (for example by utilizing suitable triage techniques), from this product, removing and to reclaim (a) if any, excessive particle, and (b) if any, may be present in the fine powder in this product.

Another embodiment of the present invention is the technique for the preparation of the brominated styrene base polymer of polymer melt or polymer flow volume morphing, this polymkeric substance typically has the bromine content at least about 50wt%, preferably at least about 60wt%, more preferably at least about 67wt%, this technique comprises:

Thereby the catalyzer cancellation is formed the as previously mentioned organic phase and the water that (ii) comprises hydrogen halide of the brominated styrene base polymer of bromine content of having that (i) comprises dissolving;

These are mutually separated from one another, and preferably make the organic phase of the brominated styrene base polymer that comprises dissolving pass through coalescence filtration;

The organic phase that will comprise the brominated styrene base polymer of dissolving is concentrated into the viscosity that is applicable to the devolatilization forcing machine;

The organic phase that will comprise the brominated styrene base polymer of dissolving is introduced the liquid-inlet part of the devolatilization forcing machine of running continuously, this forcing machine have liquid-inlet part and polymer melt or polymer fluid exit portion and can (a) under the temperature that differs from one another, at least two parts that (b) under the pressure that differs from one another, turn round, one of this at least two parts is arranged in another upstream of these at least two parts, and this devolatilization forcing machine has the vapor collection device that is suitable for being collected in the volatile matter that forms in these at least two parts;

By allowing or make the bar in this movement (for example to solidify, fully reduce by the temperature that allows or make this bar in moving) and broken, divide again or otherwise be converted into brominated styrene base polymer particle, this bar (is for example granulated, by reaching ambient air above the extraction bar on the net downwards at travelling belt or the vacuum system that provides off the net, and by jet water course being applied to downwards just on travelling belt or online mobile bar, apply enough power and make at least part of breakage of bar, the porousness of this band or net makes water be passed through net downwards, but the hole is enough carefully with fragmentation, divide again or become granular polymkeric substance strip thing to be retained in this band or online, and make fragmentation, divide or become granular polymkeric substance strip thing from this band or fall into particle sizer on the net, the impact that falls generation may cause bar to produce some other breakages); And

Particle is graded into uniform size (for example by utilizing suitable triage techniques), from this product, removing and to reclaim (a) if any, excessive particle, and (b) if any, may be present in the fine powder in this product.

The devolatilization forcing machine

In implementing various techniques of the present invention, can successfully transform commercially available devolatilization forcing machine and be used for putting into practice these technique.This forcing machine can have single screw-rod structure, parallel dual-screw structure or counter rotating double screw structure.The preferred non-engagement reverse rotation of twin screw devolatilization forcing machine.This device should have the liquid-inlet part that is positioned at the forcing machine feeding part and polymer melt or the fluid outlet part that is positioned at the extruder discharging part.It also should have at least two housing parts along spiro rod length, and preferred four with upper housing portion, its can (a) independently running under and the pressure (preferred adjustable pressure) that (b) differs from one another lower in the temperature that differs from one another (preferred adjustable temperature).At least some midstream or downstreams part must can provide the sufficiently high internal temperature will be for polymer melt or the polymer fluid of the brominated styrene base polymer of this device with formation, and preferably all parts can be like this.Typically have the ability to change up to about 350 ℃ temperature.Aspect the temperature of setting part that polymer melt or polymer fluid processed by this device therein or zone, naturally should consider in this device by fricative heat.Make in addition at least some midstream or downstreams part, preferably all parts are adapted at approximately independently running under 1 the pressure of decline in the about 500mm Hg scope.The devolatilization forcing machine should use together with the vapor collection device that is suitable for collecting whole volatile matters that every part forms.Pitch along flighted screw elements should be suitable for providing the Continuous Flow of forcing machine inclusion so that productivity is maximum.If necessary or wish, because the feature of pending concrete brominated styrene base polymer, screw element can also comprise for more well-mixed reverse thread parts and/or produce the columnar part of sealing.The manufacturers of this device can transform type and/or the pitch of screw rod, so that in case the specific brominated styrene base polymer sample of packing into and processing in suitable devolatilization forcing machine obtains gratifying flowing and mixing rate.Put into practice at least some techniques of the present invention although can be used as periodical operation, for example reclaim the technique of brominated styrene base polymer from solution, devolatilization forcing machine continuous operation is particularly preferred drive manner.

The devolatilization forcing machine device that can use the manufacturers by this equipment to provide.

Comprise anyone of devolatilization forcing machine, its design and operation for being unfamiliar with forcing machine, those of ordinary skills know and the more details utilized can be with reference to Chris Rauwendaal, PolymerExtrusion (extruding of polymkeric substance), the 4th edition, Hanser Gardner Publications, Inc., Cincinnati, Ohio.In addition referring to U.S. Patent number 3,082,816 and 4,110,843.

Illustrative selection process embodiment

Divide at suitable temperature and pressure to plant running devolatilization forcing machine, bromizate anionic styrenic polymer and in initial upstream portion, be substantially free of solvent, and if in middle reaches and/or downstream part, become not melting, then at least highly softening.Thereby the variation of the temperature distribution that adopts will be depended on the composition of the brominated anionic styrenic polymer of processing a little.

Make extrudate from this device by die head and allow the continuous bar of gained to drop on the mobile perforated conveyor belt.

Make and to fall into particle and fine powder classifier separated from one another from inclusion and any previous inclusion of this travelling belt of this newborn band of the end of travelling belt.This lower junk that drops on the classifier also can cause occuring some breakages.Classifier for example can comprise the vertically mesh of the substantial horizontal of double vibrations distribution.Suitable such device is for example can be from the vibration separation device of Witter company (The Witte Company, Inc.) acquisition especially.

In typical operation, approximately 14 feet long of used travelling belts, and with approximately 100 speed runnings in the about 200 feet per minute clock scopes.Typically, pressurizing air G﹠W used in the mist of bar is in ambient room temperature, if but wish can heat in order to reduce thermal shocking.Fall spacing on the sieve of classifier from the end of travelling belt typically approximately 18 in about 36 inches scope.

Suitably implement in the granulating process of the present invention any, with the charging of the 50wt% solution of brominated anionic polystyrene in bromochloromethane as the devolatilization forcing machine, the brominated anionic polystyrene has at least the bromine content of 50wt% (preferred 60wt% at least, more preferably 67wt% at least), might produce a kind of product, about 5wt% at the most wherein, preferred about 3wt% at the most, more preferably at the most approximately 1wt% be fine powder or dust by No. 40 USS sieves.Thereby granulating process of the present invention is very efficient; Only have very small amount of this fine powder to be collected and preferably recirculation in whole granulation operation.

Turn to now accompanying drawing, Fig. 1 with the skeleton diagram formal description be included in many steps in the preferred technological operation of the present invention, the specific embodiment according to adopting can adopt some of them or whole described step.Order described in Fig. 1 is typical, but separating step, washing step or other similar treatment step are for example inserted in the variation that can suit in this order or interpolation, does not show in Fig. 1.Thereby as long as implement devolatilization as IX place, embodiment of the present invention can be from IX or any stage more than it, and as long as acquisition according to result of the present invention, can from the description order, insert or omit more than the IX and/or the following stage.As by shown in Figure 1, embodiments more of the present invention from I styrenic polymer bromination to form the brominated styrene base polymer.Randomly can from reaction mixture, remove hydrogen halide (HBr or HCl) byproduct.Perhaps the hydrogen halide byproduct is retained in and plays solubility promoter in the reaction mixture.When reaching the degree of bromination of hope, make catalyst deactivation as II by adding suitable quantity of water, stop the aromatics bromination reaction.When the hydrogen halide byproduct is retained in the reaction mixture, in closed system, finish this catalyst deactivation, this system turns round that the hydrogen halide byproduct is retained in the reaction mixture under pressure, just adopting this technology to replace discharging and collect this byproduct in before operation.In both cases, such as III, water or the water that contains other composition such as S-WAT make to have all or the only reaction mixture cancellation of a part of byproduct HX.Hydrogen halide is recovered as Hydrogen bromide or hydrochloric acid.The preferred order that adopts II and III.Yet, may get rid of II and as III by implementing cancellation in reaction mixture suction water or the moisture S-WAT.Such as IV water phase separated and organic phase.Then can wash the organic phase that comprises the brominated styrene base polymer with moisture alkali such as aqueous sodium hydroxide washes such as V, remove residual HBr and/or HCl.

In some preferred embodiments, wish such as VI, make typically basically solution by maximum approximately 40wt% brominated styrene base polymers in organic solvent add organic phase that some residual water and salt forms through coalescence filtration, from organic phase, remove the salt of water entrainment and dissolving.Continue in some embodiments of the present invention the processing of this organic phase.In other embodiments, with typically basically by the organic phase of the solution composition of maximum approximately 40wt% brominated styrene base polymers in organic solvent as the raw material of extruding for devolatilization, its can through or without coalescence filtration.In this case arbitrary, the organic phase as VII is concentrated so is typically removed the suitable part of organic solvent to form the mixture that can extrude viscosity by distillation or flash distillation from mixture of organic phase.The preferred solvent of removing from this mixture that reclaims supplies again to utilize.Have the sufficiently high brominated styrene base polymer of molecular weight so that generation has had in the embodiment of the mixture that can extrude viscosity at initial mixture of organic phase, can get rid of this enrichment step of VII.Can extrude the mixture of viscosity in processing with before the realization devolatilization in the devolatilization forcing machine, wish this mixture of preheating as VIII.If the devolatilization forcing machine is equipped with the preheating parts, can in the devolatilization forcing machine, implement this preheating, if perhaps unequipped preheating parts of devolatilization forcing machine can independently implemented in preheater vessel or the zone.This preheating typically promotes the running of devolatilization forcing machine, thereby is preferred in this technique.

In some embodiments of the present invention, after implementing V, VI or VII, continue to process this mixture of extruding viscosity, and in other embodiments such mixture is used as starting raw material.In this case any, preferably after warp concentrates formation as VII at least, as IX, in the devolatilization forcing machine, process the mixture that to extrude viscosity, form melt or the fluid of brominated styrene base polymer and preferably be recovered and concentrate the independent gas phase that supplies again to be used as the organic solvent of solvent.This melt or fluid such as X-A are reclaimed through product or as X-B through granulating, perhaps a part of melt such as X-A reclaim through product and another part (typically all the other whole melts or fluids) such as X-B through granulation.Reclaiming such as the product the X-A can be as collecting or retrieving from the brominated styrene base polymer melt of devolatilization forcing machine or the fluid simple.The preferred method of granulation operation is implemented in Fig. 2 and 3 explanations.

Now, as for the described preferred system that comprises granulation schematically in Fig. 2 (top view) and 3 (side-views), wherein same numeral is described same part, the mixture that can extrude viscosity is sent into the import 12 of the devolatilization forcing machine 11 that preheating parts (not shown) is housed from pipeline 10, this mixture comprises the brominated styrene base polymer that typically contains 50wt% bromine at least, preferred brominated anionic styrenic polymer and solvent, preferred halogenated solvent.Equip if not so devolatilization forcing machine 11, preferably this mixture is delivered to independently preheater or preheater zone (not shown).In this case any, preferably this mixture is preheating to the temperature in about 165～approximately 185 ℃ of scopes, then in the devolatilization forcing machine, process, in order to make this mixture devolatilization by the pressure that applies enough heat and descend, other volatile matter that for example is substantially free of halogenated solvent and may exists.According to the design of devolatilization forcing machine 11, can most of volatile matter be discharged by the discharge outlet that is positioned at import 12 rears.In any case, more downstream at devolatilization forcing machine 11, the inclusion of forcing machine reaches flowable semi-solid state as polymer melt and/or the polymer fluid of brominated styrene base polymer, and this melt or fluid are discharged from by die head 18, thereby the bar (typically continuous bar) of polymkeric substance is expressed on the mobile travelling belt 20 from die head.In described system, make and be with 20 to be inclined upwardly, so that the upper distal end of band typically approximately 18 arrives approximately 36 inches on vibration separation device 30.Be typically expressed as 33 thin drip apparatus and form water smoke or carefully drip and it is assigned on the thermopolymer bar that is positioned at 20 tops, this band moves along the direction shown in the arrow 35.Then the bar of cooling is with 20 to be transported to below the air knife 37,37, and this air knife is cut apart at least a portion of bar or is broken for particle.Are vacuum inlet 39,39 of conventional vacuum manifold system (not shown) in the position of being with 20 downsides near air knife 37,37, this system extracts residual water and fine powder out from the downside with 20.The gained particle be discharged from 20 outer end, top and impact at gravity under to drop on can be on the operation end face of classifier 30 of vibration separation device.From with the 20 bulk Breakage Processes that fall, the impact that falls may cause forming extra particle.Thereby the particle in system described in Fig. 2 and 3 is mainly extending from air knife 37,37 and is comprising in the zone of classifier 30 and forming.Fine powder is graded device 30 and separates also collection within it, the particle that will keep after classifier will separate is transported to transport unit 40 continuously as on segmentation travelling belt or the chapelet, this is set installs to receive particle and also this particle is sent to forward and upwards and is suitable for particle is delivered to suitable heavy wrapping container 50 such as the height of Supersack or Gaylord container.If because particle forms any fine powder, the height of falling packaging vessel from transport unit by reduction can make it reduce or eliminate in this packaging step.

Fig. 4 is the preferred step order figure that the whole technique of the present invention of producing undoped brominated styrene base polymer granule or lozenge is adopted in explanation.Relate to Fig. 1 and be equally applicable to Fig. 4 about the above description that forms particle, except final step.In Fig. 4, final step relates to adopts proper step and device to form granule or lozenge.

Employing provides many important technology and economic advantages such as the combination that forms granule or lozenge after the obtainable device devolatilization in free market.At first, adopt this combination operation to need not ultra-large type (for example 16, the 000 gallons) settling bath that the brominated anionic styrenic polymer is precipitated out in hot water from reactive material.Do not need in addition other related part yet, for example be used for reclaiming the whizzer of solid and being used for the large-scale moisture eliminator of drying products from liquid phase.Getting rid of this large-scale plant also makes whole technique turn round in less space.In addition, significantly reduced the production cost that comprises required heat energy, the most of solvent solvent of devolatilization forcing machine (namely from) that is used for this technique can recirculation and need not drying, and whole technique has the additional capabilities of removing from the volatile impunty that is formed at last running in this technique or byproduct.For example, during operate continuously or repeating periodical operation, the preferred bromochloromethane of small portion solvent is converted into methylene bromide, and it is very favorable at least regularly removing this material from the solvent of recirculation this technique.

The illustrative commercially available device that is applicable to form granule or lozenge is the Pastillation System by name that can obtain from KaiserSteel Belt Systems GmbH company System.Not only can be from the publicity materials that Kaiser Steel Belt Systems GmbH company obtains, and at U.S. Patent number 5,198, this class device and operation thereof have been described in 233 and 5,278,132.

Analytical procedure

If think essential or hope, in determining this analysis or character, can adopt any reliable analytical procedure of reporting as in the literature.In office what indefinite or the arguement situation under, recommend following method:

1) bromine content: because the brominated styrene base polymer has good or gratifying at least solubleness in solvent such as tetrahydrofuran (THF) (THF), easily finish the mensuration of total bromine content in the brominated styrene base polymer by adopting conventional XRF technology.The sample of analyzing is dilute sample, i.e. 0.1 ± 0.05g brominated Polystyrene among the 60mL THF.The XRF spectrograph can be Phillips PW1480 spectrograph.Bromobenzene standardized solution in THF is used as calibration standard.

2) crushing strength: Sintech 1/S compressing device (MTS Systm Corp. (MTS Systems Corporation) that Testworks software is housed is adopted in the crushing strength experiment, Edenprairie, the Minnesota State), this software is installed in the 1/S compressing device by the indication of MTS Systm Corp..The 1/S compressing device comprises the horizontal load sensor that is connected with computer, the digital micrometer that is connected with computer equally and is arranged in the vertical screw transmission ram that is suitable for applying above the load transducer perpendicular to the downward power of load transducer.The step of measuring crushing strength comprises the length of measuring particle with micrometer, provides the digitizing input to computer.Next the particle end is placed on the load transducer, piston is contacted with the upper limb of this particle.Then starter gear, piston begin to apply the downward power that improves gradually to particle.Simultaneously, load transducer is measured the downward power that is applied to particle continuously, and the input of this measuring result is transferred to computer.When the value that reaches power when the power that applies was reduced to suddenly 10% point of last power, particle reached breaking point, stops immediately applying power by software program.Result by the input computer provides two numerical value, i.e. the poundage of power when the breaking point of particle, and when this breaking point the poundage of the power of per inch length particle.Thereby the power that applies is larger, and crushing strength is larger.In this experiment, select at random 13 particles and be used for this experiment.Unique requirement is that selected particle should have smooth end in order to keep flat and vertically stand on the load transducer, and has the smooth top of horizontal fitting piston bottom surface.

3) molecular weight and polymolecularity: adopt Waters model 510 HPLC pumps and as the differential refraction detector (Refractive Index Detector) of the Waters company of wave-detector, the light scattering detector of Model 410 and Precision Detector company (Light Scattering Detector), the device of ModelPD2000 or equivalence obtains the values for molecular weight of styrenic polymer by GPC.Post is that Waters company makes, μ Styragel,

With

Self-actuated sampler is that Shimadzu company makes Model Sil 9A.Periodically use the precision of polystyrene standards (Mw=185,000) verification light scattering data.Used solvent is tetrahydrofuran (THF), the HPLC level.Used experimental procedure need to be with 0.015～0.020g sample dissolution in 10mL THF.Filter the aliquots containig of this solution, and 50 μ L are expelled on the post.This separation of software analysis that is used for PD 2000 light scattering detectors of adopting Precision Detectors company to provide.This instrument provides the result according to weight-average molecular weight and according to number-average molecular weight.Thereby, in order to obtain the numerical value of polymolecularity, use the value of weight-average molecular weight divided by the value of number-average molecular weight.

4) in order to determine to be retained in the organic solvent amount in the brominated styrene base polymer sample, adopt BrukerDPX 400 MHZ instruments to about 20wt% brominated styrene base polymer solution by 5/2 dithiocarbonic anhydride/methylene chloride volume ratio-d ₂(one 30 degree pulse test, 8 line scannings and 15 pulse per second (PPS)s time-delay) obtains proton NMR spectrum.Obtain simultaneously the integration of brominated styrene base polymer and the integration of organic solvent component.Adopt suitable values for molecular weight and this integration, calculate the organic solvent amount in the polymkeric substance.

Continuous processing

Although technique of the present invention can be used as batch technology and implements, wherein process the charging of specified rate, technique of the present invention is preferably implemented in then shut-down operation continuously, only periodically shut-down operation for example in order to overhaul or care device.The preferred continuous processing of the present invention is produced high-purity bromination free radical styrenic polymer melt or fluid, perhaps high-purity bromination free radical styrenic polymer particle.The particularly preferred continuous processing of the present invention is produced high-purity brominated anionic styrenic polymer melt or fluid, perhaps high-purity brominated anionic styrenic polymer particle.To these continuous processings general be with described some or all operations of skeleton diagram form in Fig. 1.

Particle of the present invention

According to the present invention, produce granular brominated styrene base polymer, even having, it also only has a small amount of fine particle or dust.

New particle of the present invention is comprised of the preferred undoped brominated anionic polystyrene of undoped brominated anionic styrenic polymer, and it has following feature:

A) at least about the bromine content of 50wt%, preferably at least about 60wt%, more preferably at least about 64wt%, and more preferably in about 67 to about 71wt% scope;

B) in crushing strength experiment at least about 28 pounds/square inchs average crushing strength, and preferably at least about 32 pounds/square inchs;

C) size range, wherein at least about 70wt% and preferably be retained on No. 40 USS sieves at least about the particle of 75wt%, and at the most approximately 30wt% and preferably at the most approximately 25wt% be retained on No. 5 USS sieves.

More preferably particle at least about 80wt%, also more preferably at least about 85wt%, and even more preferably be retained on No. 40 USS sieve at least about 90wt%, and 20wt% more preferably from about respectively, more preferably about 15wt% at the most also, and even more preferably at the most approximately 10wt% be retained on No. 5 USS sieves.

By utilizing the producible granule of the present invention or lozenge

In order to simulate technique of the present invention, produce lozenge and process experiment and determine their crushing strength.Adopt Rollormat granulating system (Kaiser Steel Belt Systems) to bromizate anionic polystyrene through granulation, it has about 68% bromine content and the melt flow index under 220 ℃ and per 10 minutes load of 2.16 kilograms of 4 to 35 grams.Form basically uniform lozenge, and solidify at the mobile steel band of water-cooled.The sample of collecting these lozenge is used for measuring physicals.Particularly test to measure the height of 13 random lozenge of selecting in described technique just now, producing and the crushing strength of selected lozenge.The device that is used for these experiments is Sintech 1/S instrument.Used step comprises following:

1) 13 lozenge of random selection from the sample that stands to test, and measure each lozenge from its flat height to its dome peak;

2) lozenge is placed on the fixing linerless steel plate of this instrument, the flat surface of this lozenge is placed on the steel plate, and the dome peak that makes this lozenge connects 50 pounds of load transducers directly below the pinblock of this instrument activity on this pinblock.What connect load transducer is cylindrical shaft, and its lower end that will directly contact with the dome peak of lozenge is smooth;

3) pinblock is reduced in 0.002 inch of this dome peak;

4) by this instrument of speed mechanize worm drive with 0.2 cun per minute this pinblock is fallen, until crushing lozenge in this some record ultimate load, and is pressed the pound per inch and calculated crushing strength.

Repeat above step with being selected from random through in 13 lozenge of the lozenge sample of experiment each respectively.By determining crushing strength separately in 13 kinds of situations with overall loading (pound) except the height (fraction of an inch is very little) of each lozenge that stands to test.

Table 1 has been summarized the result of 13 single experiments, the standard deviation of the average that obtains in experiment, the numerical value of acquisition and minimum and the maximum value of acquisition.In table 1, for conserve space with granule or lozenge referred to as lozenge.Used abbreviation and their full sense are as follows: in. represents inch; Lbs. represent ft lbf; Avg. representative is average; Std.Dev. represent standard deviation; Min. represent minimum; And Max. represents maximum.

Table 1

Particle or granule or lozenge are as the purposes of fire retardant

Particle of the present invention and granule/lozenge of producing according to the present invention can be used as fire retardant in multiple thermoplastic polymer.This polymkeric substance comprises thermoplastic polyester, such as polyethylene terephthalate, polybutylene terephthalate, Poly(Trimethylene Terephthalate), poly terephthalic acid cyclohexanediol ester etc.; Polyamide thermoplastic is such as nylon 6, nylon 6,6, nylon 6,12 etc.; Polycarbonate; Polyphenylene oxide is such as poly-(the inferior phenylate of 2,6-dimethyl); Polysulfones; Polystyrene or other styrenic homopolymer; The multipolymer of two or more styrenic monomers is such as the multipolymer of vinylbenzene, Vinyl toluene, ethyl styrene, t-butyl styrene, alpha-methyl styrene, vinyl naphthalene etc.; The aromatic vinyl homopolymer of modified rubber or multipolymer (for example, high-impact polystyrene); Acrylics or methacrylate based polymers are such as ethylene-methyl acrylate, ethylene-propylene acetoacetic ester, ethylene-propylene acid butyl ester, poly-(methyl methacrylate) etc.; Ethylene-vinyl acetate copolymer; Acrylonitrile copolymer and terpolymer are such as acrylonitrile-butadiene-styrene (ABS) (ABS) and styrene-acrylonitrile (SAN) etc.; Polyolefine is such as the multipolymer of polyethylene, polypropylene, poly-(1-butylene) and ethene and more than one high-stage ethylene base alkene such as propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene; And the mixture of different polymkeric substance, adulterant or matrix material, for example mixture of mixture, polycarbonate and the polystyrene of poly-(the inferior phenylate of 2,6-dimethyl) and polystyrene and similarly mixture.By adopting simultaneously other polymkeric substance that granular fire-retardant additive of the present invention can be fire-retardant to include elastic segmented copolymer such as styrene-ethylene-ethene-vinylbenzene, styrene-ethylene-propylene-styrene, styrene-ethylene-butylene-styrene etc.; Urethane; Resins, epoxy; Resol; Elastomerics such as natural rubber, isoprene-isobutylene rubber, GRS, GRN, EPDM etc.; Polysiloxane etc.In addition, can suitably make crosslinked polymer by chemical process or by radiation.The polymkeric substance that does not conform in a large number fire retardant that is applicable to the present invention's practice can obtain from many commercial source.

Polyester by utilizing can be the effectively fire-retardant preferred matrix polymer group of particle of the present invention.The thermoplastic polyester that is commonly called polyalkylene terephthalates is aromatic dicarboxylic acid or its reactive derivative, such as methyl esters or acid anhydrides, with the reaction product of aliphatics, cyclic aliphatic or aromatic-aliphatic glycol (araliphatic diols), and the mixture of this reaction product.The example of this thermoplastic polyester comprises polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate, poly terephthalic acid hexamethylene dimethyl ester and relevant copolyesters and mixture, comprises the particularly mixture of aromatic polycarbonate of more than one thermoplastic polyesters and more than one other thermoplastic polymers such as polycarbonate.

Preferred thermoplastic polyester based on the dicarboxylic acid component, comprises at least preferably 90wt% terephthalic acid at least of 80wt%, and based on diol component, comprises at least 80wt% preferably at least 90wt% ethylene glycol and/or BDO unit.

Except terephthalic acid units, preferred thermoplastic polyester can comprise maximum 20 % by mole of preferred other maximum 10 % by mole aromatics or cyclic aliphatic C _8～14Dicarboxylic acid or aliphatics C _4～12Dicarboxylic acid, for example phthalic acid, m-phthalic acid, NDA, 4,4 '-unit of diphenyl dicarboxylic acid, Succinic Acid, hexanodioic acid, sebacic acid, nonane diacid or hexanaphthene Succinic Acid.

Except ethylene glycol and BDO unit, preferred thermoplastic polyester can comprise maximum 20 % by mole of preferred maximum 10 % by mole other aliphatics C _3～12Glycol or cyclic aliphatic C _6～12Glycol, for example 1,3-PD, 2-ethyl propane-1, the 3-glycol, neopentyl glycol, 1,5-PD, 1,6-hexylene glycol, 1,4-hexanaphthene-dimethanol, 3-ethylpentane-2, the 4-glycol, 2-methylpentane-2, the 4-glycol, 2,2,3-trimethylpentane-1, the 3-glycol, 2-ethyl hexane-1, the 3-glycol, 2,2-diethyl propane-1, the 3-glycol, 2,5-hexylene glycol, two (4-hydroxyl-cyclohexyl) propane of 2,2-, 2,4-dihydroxyl-1,1,3,3-tetramethyl-ring butane, 2, two [4-(2-hydroxyl-oxyethyl group) phenyl] propane of 2-or 2,2-be two-unit of [4-hydroxyl propoxy-) phenyl] propane.

By ternary or tetravalent alcohol or tricarboxylic acid or tetracarboxylic acid in conjunction with relatively small amount, polyalkylene terephthalates can be by branching.In this connection referring to for example U.S. Patent number 3,692,744.The example of preferred branching agent is trimesic acid, trihemellitic acid, trimethylolethane and TriMethylolPropane(TMP) and tetramethylolmethane.Particularly preferred thermoplastic polyester is only by terephthalic acid or its reactive derivative, such as dialkyl, and the thermoplastic polyester of producing with ethylene glycol and/or Isosorbide-5-Nitrae-butanediol, and the mixture of these polyalkylene terephthalates.Preferred polyalkylene terephthalates mixture comprises 1 to 50wt% polyethylene terephthalate and 99 to the 50wt% polybutylene terephthalate.Particularly preferred polyalkylene terephthalates mixture comprises 1 to 30wt% polyethylene terephthalate and 99 to the 70wt% polybutylene terephthalate.

As adopting the Ubbelohde viscometer measured in phenol/orthodichlorobenzene (1: 1 weight part) under 25 ℃, preferred used polyalkylene terephthalates has 0.4 to 1.5dl/g limiting viscosity usually, preferred 0.5 to 1.3dl/g, and more preferably 0.55 arrive 1.2dl/g.The most preferably polyethylene terephthalate of these limiting viscosity scopes and polybutylene terephthalate and composition thereof.As everyone knows, the polyethylene terephthalate engineering resin producer is by pure PET (typically 0.55～0.70IV) or from synthetic their product of the regenerative PET of industrial waste, polyester film waste material, bottle and a small amount of trevira waste material.

Operable other thermoplastic polyester comprises for example thermoplastic polyester of polyether ester, polyester-polycarbonate mixture or adulterant, polyester-MBS mixture or adulterant and impact modification in practice of the present invention.

Can be by known method production polyalkylene terephthalates.Referring to for example Encyclopediaof Polymer Science and Technology (the polymerization science and technology is complete works of), 11 volumes, 62～128 pages, John Wiley﹠amp; Sons, Inc. (John Wei Li publishes company limited), 1969 editions; And Kirk-Othmer, Encyclopedia of Chemical Technology (Chemical Engineering Technology encyclopedia), 4th Ed., Vol.19,609～653 pages, John Wiley﹠amp; Sons, Inc. (John Wei Li publishes company limited), 1996 editions.

The polymeric amide that sometimes is called as nylon polymer by utilizing can be effectively fire-retardant another of particle of the present invention to organize preferred thermoplastic polymer.This polyamide matrix polymkeric substance can be any unbodied and/or partial crystallization mainly be aliphatics/cyclic aliphatic or partially aromatic polyamide thermoplastic.Typically, by by mainly or all being partly or entirely to be mainly or all to be partly or entirely to be that the carboxylic acid of aromatics or polycondensation and/or the polymerization technique of lactan are produced this material on aliphatics or cyclic aliphatic or the structure on the diamines of aromatics and the structure on aliphatics or cyclic aliphatic or the structure on the structure.The typical amine that is used to form polymeric amide comprises diamines, such as hexamethylene-diamine, tetramethylene-diamine, 2,2,4-and 2,4,4-trimethylammonium-hexamethylene-diamine, diamino-dicyclohexyl methane (isomer), diamino dicyclohexyl propane (isomer) and isophorone diamine (isomer) and xylylene amine.Also be used as having of raw material: aminocarboxylic acid such as epsilon-amino caproic acid, perhaps omega-amino-carboxylic acid such as omega-amino-lauric acid and omega-amino-undecanoic acid.Typically, used carboxylic acid is aliphatics or has aliphatics-aromatic dicarboxylic acid less than the mixing of 50wt% aromatics composition, such as hexanodioic acid, 2,2,4-and 2,4,4-trimethyladipic acid, nonane diacid, sebacic acid, decane dicarboxylic acid, dodecanedicarboxylic acid, cyclohexane dicarboxylic acid, hexahydroterephthalic acid, m-phthalic acid and terephthalic acid.

Can also adopt the copolyamide from most of known monomers.

The illustrative polymeric amide that can be used for the present invention practice is for example nylon 6, nylon 6,6, nylon 6,9, nylon 6,10, nylon 6,12, （Fen Mo/Ke Li） Nylon11 in powder/granular form, nylon 12,

nylon

12,12, nylon 6/6,6 multipolymers, and high-temperature nylon such as nylon 4,6, and this polymeric amide of partially aromatic nylon (for example, from the Ixef polyarylamide PA MXD6 of Solvay company, from the Zytel HTN of E.I.Du Pont Company with from the Amodel polyarylamide of Solvay company).Other polymeric amide that can adopt comprises from the polyamide 6 T of the Arlen modification of Mitsui Chemicals, Inc., from the Genestar PA9T polyamide resin of Kuraray company, from the Stanyl polymeric amide 46 of DSM (DSM) company, from the Vydyne polyamide 6 of Monsanto Company (Monsanto)/66 multipolymers, polyamide 612 (from the Vestamid D of Creanova company) and similar polymeric amide.In various nylon polymers, nylon 6 and nylon 6,6th, preferred matrix polymer.

The present invention also can be applicable to thermoplastic mixture or the adulterant of more than one polymeric amide, polyamide-polyolefin mixture or adulterant, polymeric amide-contain polymeric blends or adulterant, polymeric amide-ABS mixture or adulterant, polymeric amide-EPDM mixture or adulterant, polyamide-polyphenylene ether mixture or adulterant, the perhaps polymeric amide of impact modification of ionic linkage for example.

Method for the production of polyamide polymer is known and is described in the literature.Referring to for example Encyclopedia of Polymer Science and Technology (the polymerization science and technology is complete works of), 10 volumes, 460～482 pages, John Wiley﹠amp; Sons, Inc. (John Wei Li publishes company limited), 1969 editions; And Kirk-Othmer, Encyclopedia of Chemical Technology (Chemical Engineering Technology encyclopedia), 4th Ed., Vol.19,559～653 pages, John Wiley﹠amp; Sons, Inc. (John Wei Li publishes company limited), 1996 editions.

Enforcement and the advantage of the following example explanation one embodiment of the invention.This embodiment does not limit general range of the present invention.

Embodiment

The devolatilization forcing machine that is used for this operation is Werner﹠amp; Pfleiderer ZSK-30 30mm parallel dual-screw extruding machine.This machine has nine barrel configuration of length-to-diameter ratio 27/1.At machine barrel 4 discharge outlet is set, and provides a discharge outlet to be used for machine barrel 8 is applied 30 inches vacuum tightnesss.Provide vacuum to reduce trap (vacuum knockdown trap) with the concentrated volatile matter that leaves from the discharge outlet of machine barrel 4.Operate this device by following temperature distribution: feed throat is opened water coolant, 140 ℃ in 1 district, 180 ℃ in 2 districts, 220 ℃ in 3 districts, 240 ℃ in 4 districts.Die head in this outlet is retained in 230 ℃.Screw design provides mild kneading parts at machine barrel 5 and 6.Operational condition is 125rpm and 30% moment of torsion, have 243 ℃ melt temperature and brominated anionic polystyrene (by

HP 3010 forms, Albemarle Corporation) feeding rate of the 8kg/hr of 83% solution in bromochloromethane (BCM).Two bars are expressed on the traction band-type transfer roller that is five feet long, and automatic transport is to the open drum that is in this end of tape.Take out sample from open drum.Because it is limited to can be used for the brominated anionic polystyrene material amount of this operation, this machine operation approximately 8～10 minutes.Material is mobile glibly during operation.Reduce concentrated approximately 20～30mL BCM solvent in the trap in vacuum.Adopt dry ice and Virahol cooling vacuum trap, even this also is enough to concentrated BCM under the vacuum tightness of used 30 inches Hg.The devolatilization non-impurity-doped brominated anionic granules of polystyrene of producing has good outward appearance and has enough thickness so that place several holders (carrying wherein two) and do not have obvious Particle attrition.

The whole system that adopts among this embodiment is schematically described in Fig. 2 and 3.In this system, adopt lower array apparatus:

A) fully equipment and break-in described in this embodiment of devolatilization extruder system 11.

B) die head 18 is the diplopore moulds with 4mm diametric hole.

C) travelling belt 20 is the length with 14 feet (about 4.3 meters), the width of 15 inches (approximately 38.1cm) and the Scheer-Bay travelling belt of 3 inches (about 7.6 centimetres) diameter rollers.This guipure is inclined upwardly with about 12 ° angle.

D) classifier 30 is Witte model no 200 classifiers.

Be approximately 24 inches (approximately 61cm) from the vertical range between the top of falling classifier 30 with 20 end, and the vertical range between the bottom of the end of transport unit 40 and container 50 (empty) is approximately 60 inches (approximately 152cm).Travelling belt moves with the speed of 150 to 175 feet per minute clocks (about 45.7 to about 53.3 m/mins).Water smoke is with the approximately speed charging of 1 gallon per minute (about 3.79 liter/mins of clocks).Under 10～25 pounds/square inchs pressure, operate air knife, and air knife is arranged in approximately 5 inches (approximately 12.7cm) on the travelling belt surface.Be applied to vacuum tightness below the travelling belt and be approximately 2200 cubic feet/min (about 62.3 cubic meters per minute), and by with two vacuum applicator (vacuum applicators) of lateral arrangement next-door neighbour's travelling belt surface is directly applied vacuum, the mouth of each applicator has the area of 45 square inches (about 114.3 square centimeters).

For the intensive property of obtainable raising in particle of the present invention is described, be displayed in Table 2 by by the brominated anionic Polystyrene powder that is dissolved in the bromochloromethane solvent HP 3010, Albemarle Corporation) the 60wt% solution devolatilization of making divide the particle (particle of the present invention) of extrusion and do not have with this solution devolatilization divide extrude and replace as described in the disclosed PCT patent application WO2005/118245 that owns together with brominated anionic Polystyrene powder (SAYTEX HP 3010, Albemarle Corporation) the crushing strength data of the particle of extrusion (non-particle of the present invention), particle has good quality.

Table 2

The component of in this paper specification sheets or claim, mentioning with chemical name or chemical formula, no matter mention with odd number or plural number, regard as and just exist before with the another kind of material of mentioning with chemical name or chemical type (for example, another kind of component, solvent or thinner etc.) contact.No matter what primary chemical occurs in gained mixture or solution or reaction medium change, transform and/or the reaction (if there is), these change, transform and/or reaction is the normal result who under the condition that requires according to the disclosure specific reactant and/or diversity is combined together.Thereby this component is counted as relevant with the operation of carrying out hope or the composition of form wishing and batching that be pooled to together is the same.In addition, even may mention material, component and/or composition with present tense (" comprising ", "Yes" etc.) in the claim hereinafter, connotation be material, component and/or composition as it according to other material of the disclosure and more than one, component and/or composition contacts at first, fusion or mix before the state that exists.If implement according to the disclosure and by those of ordinary skills, by chemical reaction or conversion, perhaps material, component or composition have lost its initial characteristic in contact, fusion or married operation process, and this fact does not have actual impact.

Each patent that this specification sheets any part is mentioned or other publication or disclosed document are incorporated the disclosure by reference into, just as this paper fully set forth.

Unless clearly indicate in addition, and if article " a " or " an " attempt to limit and also should not be interpreted as claim is restricted to the single key element that this article relates to as used herein.More suitably, unless clearly illustrate that in addition in the literary composition, and if article " a " or " an " attempt to cover more than one this key elements as used herein.

The present invention easily carries out sizable variation in its practice.Therefore foregoing description is not to attempt and should not be construed as limiting the invention to concrete example given above.

Claims

1. be used for from reclaim the technique of brominated styrene base polymer at the mixture of volatilizable organic solvent, this technique comprises: the independently gas phase that in the devolatilization forcing machine mixture of brominated styrene base polymer is converted into brominated styrene base polymer melt or fluid and mainly comprises volatilizable solvent, from the devolatilization forcing machine, reclaim described brominated styrene base polymer melt or the fluid of melt or flow morphology, and allow or make described melt or fluid solidifies, wherein said devolatilization forcing machine has the liquid-inlet part, polymer melt or polymer fluid exit portion and can (a) under the temperature that differs from one another and at least two parts that turn round under the pressure that (b) is differing from one another, one of this at least two parts is arranged in another upstream of these at least two parts, and this devolatilization forcing machine has the vapor collection device that is suitable for being collected in the volatile matter that forms in these at least two parts.

2. technique as claimed in claim 1, wherein, described technique comprises:

The mixture that can extrude viscosity is introduced the liquid-inlet part of the devolatilization forcing machine of running continuously, and described mixture comprises brominated styrene base polymer and volatilizable organic solvent; And

Comparing the described parts that are arranged in the downstream of running under higher temperature and the lower pressure condition with the described temperature and pressure condition that is arranged in the parts of upstream, in order to (a) in the devolatilization forcing machine, form fluid or the melt of described polymkeric substance, and emit from the outlet of polymer melt or polymer fluid, and the volatile matter of the solvent composition of (b) mainly being emitted by the polymkeric substance in described at least two parts can be collected by described vapor collection device, under quiet rum, the melt or the fluid that leave this brominated styrene base polymer of devolatilization outlet of extruder part comprise the organic solvent that mean number is less than 10,000ppm (wt/wt).

3. be used for from the technique at the mixture production particulate state brominated styrene base polymer of volatilizable organic solvent, this technique comprises: can extrude the independently gas phase that the mixture of the brominated styrene base polymer of viscosity is converted into brominated styrene base polymer melt or fluid and mainly comprises volatilizable solvent in the devolatilization forcing machine, from the devolatilization forcing machine, reclaim described brominated styrene base polymer melt or the fluid of melt or flow morphology, allow or make described melt or fluid solidifies, and melt or the fluid that solidifies be converted into particle, wherein said devolatilization forcing machine has the liquid-inlet part, polymer melt or polymer fluid exit portion and can (a) under the temperature that differs from one another and at least two parts that turn round under the pressure that (b) is differing from one another, one of this at least two parts is arranged in another upstream of these at least two parts, and this devolatilization forcing machine has the vapor collection device that is suitable for being collected in the volatile matter that forms in these at least two parts.

4. technique as claimed in claim 3, wherein, by making described melt or fluid pass through die head by the devolatilization forcing machine, allow or make described melt or fluid solidifies, thereby produce brominated styrene base polymer melt or fluid new life's bar, allow or make described bar to solidify, and this bar is further divided into the brominated styrene base polymer particle of curing.

5. technique as claimed in claim 4, wherein,

Allow and/or make described bar to solidify and broken, divide again or otherwise be converted into brominated styrene base polymer particle; And

Make described particle grade into uniform size from this product, to remove and reclaim (a) if any, excessive particle, and (b) if any, may be present in the fine powder in this product.

6. technique as claimed in claim 3, wherein, described brominated styrene base polymer is the brominated anionic styrenic polymer.

7. technique as claimed in claim 3, wherein, described brominated styrene base polymer is the brominated Polystyrene polymkeric substance.

8. technique as claimed in claim 3, wherein, described brominated styrene base polymer is the brominated anionic poly styrene polymer.

9. for the preparation of the technique of the brominated styrene base polymer of melt or polymer flow volume morphing, this technique comprises:

In volatilizable solvent and in the presence of the Lewis acid bromination catalyst, in airtight reactive system under super-atmospheric pressure with the styrenic polymer bromination, in this reactive system basically all hydrogen halide byproducts be retained in the reaction mixture;

Thereby make the catalyzer cancellation form organic phase and the water that (ii) comprises hydrogen halide that (i) comprises the brominated styrene base polymer of dissolving;

Comparing the described parts that are arranged in the downstream of running under higher temperature and the lower pressure condition with the described temperature and pressure condition that is arranged in the parts of upstream, in order to (a) in the devolatilization forcing machine, form flowable polymer melt or the polymer fluid of described polymkeric substance, and emit from the outlet of at least one polymer melt or polymer fluid, and the volatile matter of the solvent composition of (b) mainly being emitted by the polymkeric substance in described at least two parts is collected by described vapor collection device, during devolatilization forcing machine quiet rum, the polymer melt or the polymer fluid that leave this brominated styrene base polymer of devolatilization outlet of extruder part comprise the organic solvent that is used for this technique that mean number is less than 10,000ppm (wt/wt).

10. technique as claimed in claim 9, wherein, the styrenic polymer for the treatment of bromination in this technique is to have 2000 to 200, GPC weight-average molecular weight (Mw) in 000 scope and at least a anionic styrenic polymer of the GPC polymolecularity in 1 to 2 scope, the brominated styrene base polymer that wherein forms in described technique has at least bromine content of 50wt%.

11. technique as claimed in claim 10, wherein, described GPC weight-average molecular weight (Mw) is in 3000 to 10,000 scope, and described bromine content is 60wt% at least.

12. technique as claimed in claim 11, wherein, described GPC weight-average molecular weight (Mw) is in 3000 to 7000 scope, and described bromine content is 67wt% at least.

13. technique as claimed in claim 9, wherein, the styrenic polymer for the treatment of bromination in this technique is to have 30,000 to 500, the styrenic polymer that at least a free radical of the GPC weight-average molecular weight (Mw) in 000 scope and the GPC polymolecularity in 1 to 10 scope is produced, and the brominated styrene base polymer that wherein forms in described technique has at least bromine content of 50wt%.

14. technique as claimed in claim 13, wherein, described GPC weight-average molecular weight (Mw) is in 50,000 to 300,000 scope, and described bromine content is 60wt% at least.

15. technique as claimed in claim 14, wherein, described GPC weight-average molecular weight (Mw) is in 150,000 to 250,000 scope, and described bromine content is 67wt% at least.

16. for the preparation of the technique of particulate state brominated styrene base polymer, this technique comprises:

In volatilizable organic solvent and in the presence of the Lewis acid bromination catalyst, in airtight reactive system under super-atmospheric pressure with the styrenic polymer bromination, in this reactive system basically all hydrogen halide byproducts remain in the reaction mixture;

Water makes catalyst deactivation, thereby forms organic phase and the water that (ii) comprises hydrogen halide that (i) comprises the brominated styrene base polymer of dissolving;

Make the continuous bar of the more than one movement of polymer melt that the described polymer melt that leaves the devolatilization forcing machine or polymer fluid extrude with generation by die head or polymer fluid;

Allow and/or make the bar of this continuous movement to solidify and broken, divide again or otherwise be converted into brominated styrene base polymer particle.

17. technique as claimed in claim 16, wherein, the styrenic polymer for the treatment of bromination in this technique is to have 2000 to 200, GPC weight-average molecular weight (Mw) in 000 scope and at least a anionic styrenic polymer of the GPC polymolecularity in 1 to 2 scope, the brominated styrene base polymer that wherein forms in described technique has at least bromine content of 50wt%.

18. technique as claimed in claim 16, wherein, the styrenic polymer for the treatment of bromination in this technique is to have 30,000 to 500, the styrenic polymer that at least a free radical of the GPC weight-average molecular weight (Mw) in 000 scope and the GPC polymolecularity in 1 to 10 scope is produced, and the brominated styrene base polymer that wherein forms in described technique has at least bromine content of 50wt%.

19. for the production of the technique of particulate state brominated styrene base polymer, this technique comprises:

The mixture that will comprise the viscosity extruded of brominated styrene base polymer and volatilizable solvent is sent into the devolatilization forcing machine, adjustment and this forcing machine that turns round are with the volatilizable solvent of separation from described polymkeric substance, and formation is as polymer melt or the polymer fluid of the described polymkeric substance of extrudate;

Make this extrudate by die head, thereby form the bar of the more than one movement of the undoped brominated styrene base polymer of melting; And

Solidify also fragmentation, divide again or otherwise be converted into brominated styrene base polymer particle by the bar that allows and/or make this movement, with this bar granulation; And

Particle is graded into uniform size, from this product, remove and reclaim (a) if any, excessive particle, and (b) if any, may be present in the fine powder in this product;

Wherein said devolatilization forcing machine have liquid-inlet part, polymer melt or polymer fluid exit portion and can (a) under the temperature that differs from one another and at least two parts that turn round under the pressure that (b) is differing from one another, one of this at least two parts is arranged in another upstream of these at least two parts, and this devolatilization forcing machine has the vapor collection device that is suitable for being collected in the volatile matter that forms in these at least two parts.

20. technique as claimed in claim 19 is characterized in that:

The mixture of the viscosity extruded by will comprising brominated styrene base polymer and volatilizable organic solvent is introduced continuously the liquid-inlet of the devolatilization forcing machine of running and is partly implemented described sending into;

Comparing the described parts that are arranged in the downstream of running under higher temperature and the lower pressure condition with the described temperature and pressure condition that is arranged in the parts of upstream, in order to (a) in the devolatilization forcing machine, form flowable melt or the fluid of described polymkeric substance, and emit forcibly from the outlet of polymer melt or polymer fluid, and the volatile matter of the solvent composition of (b) mainly being emitted by the polymkeric substance in described at least two parts can be collected by described vapor collection device, the polymer melt or the polymer fluid that leave this brominated styrene base polymer of devolatilization outlet of extruder part comprise the mean number that is less than 10,000ppm (wt/wt); Make described polymer melt or the polymer fluid of this brominated styrene base polymer that leaves devolatilization outlet of extruder part pass through described die head, form thus the bar of the more than one movement of the undoped brominated styrenic polymer of described melting.

21. undoped brominated anionic styrenic polymer particle, it is prepared by each described technique among the claim 1-20, and has following feature:

A) bromine content of 50wt% at least;

B) at least 28 pounds/square inchs average crushing strength in the crushing strength experiment;

C) size range, wherein the particle of 70wt% is retained on No. 40 USS sieve at least, and is less than 30wt% and is retained on No. 5 USS sieves.

22. produce the technique of undoped brominated anionic styrenic polymer granule or lozenge, this technique comprises:

Described melt or fluid are from the manifold that approaches the plane of motion member that cools off or the piston flow that at least one mouth of pipe the ozzle forms downward orientation, the not saturating cooling fluid of described plane institution movement also has end face and the bottom surface, thereby between the bottom of the mouth of pipe and described end face, a gap is arranged, so that at least a portion melting undoped brominated anionic styrenic polymer piston or (i) the described gap of cross-over connection and form independently single granule or lozenge at the end face of described plane institution movement, perhaps (ii) freely falls and drops on the end face of described plane institution movement from the bottom of the mouth of pipe, and forming single granule or lozenge at the end face of described plane institution movement, the member of described movement is touched the cooling fluid mist of described plane institution movement bottom surface or carefully drips cooling;

23. for the preparation of the technique of the brominated styrene base polymer of undoped brominated anionic styrenic polymer granule or lozenge form, this technique comprises:

In volatilizable solvent and in the presence of the Lewis acid bromination catalyst, in airtight reactive system under super-atmospheric pressure, with the anionic styrenic polymer bromination, in this reactive system basically all hydrogen halide byproducts be retained in the reaction mixture;

With phase (i) and (ii) separated from one another, and if phase (i) have less than the viscosity that can extrude viscosity, then that the organic phase of (i) is concentrated to form the mixture that can extrude viscosity;

Comparing the described parts that are arranged in the downstream of running under higher temperature and the lower pressure condition with the described temperature and pressure condition that is arranged in the parts of upstream, in order to (a) in the devolatilization forcing machine, form flowable polymer melt or the polymer fluid of described polymkeric substance, and emit from the outlet of at least one polymer melt or polymer fluid, and the volatile matter of the solvent composition that (b) is mainly discharged by the polymkeric substance in described at least two parts is collected by described vapor collection device;

The described flowable polymer melt of described polymkeric substance or fluid are from the approaching manifold of plane of motion member or the piston flow that at least one mouth of pipe the ozzle forms downward orientation of cooling off; the not saturating cooling fluid of described plane institution movement also has end face and the bottom surface; thereby between the bottom of the mouth of pipe and described end face, a gap is arranged; so that at least a portion melting undoped brominated anionic styrenic polymer piston or (i) the described gap of cross-over connection and form independently single granule or lozenge at the end face of described plane institution movement; perhaps (ii) freely falls and drops on the end face of described plane institution movement from the bottom of the mouth of pipe; and form single granule or lozenge at the end face of described plane institution movement, the member of described movement be touched described plane institution movement the bottom surface the cooling fluid mist or carefully drip cooling.