Polymers of Brominated Styrene

A process for the solventless polymerization of brominated styrenes includes blending monomers of brominated styrenes with a polymerization initiator, feeding the monomer/polymerization initiator mix into a prepolymerizer wherein the monomers begin to polymerize, and feeding the monomer/polymerization initiator mix and the partially polymerized bromostyrene into a screw-type extruder to drive the polymerization to a high degree of completion in a short period of time. Optionally, the monomers may be preheated before mixing with the initiator, or a heater may be included in the prepolymerizer.

SUGGESTED CITATION

Polymers of Brominated Styrene. E. J. Termine R. W. Atwell, H. A. Hodgen, W. R. Fielding and N. A. Favstritsky, United States Patent No. 5,304,618.
Available at: http://termine.com/archives/525

FIELD OF THE INVENTION

The present invention relates generally to polymers of brominated styrene, and more particularly to methods for the solventless bulk polymerization of brominated styrenes.

BACKGROUND OF THE INVENTION

A variety of polymers of brominated styrene are known to the art. These brominated polystyrenes are commonly used as flame retardant additives, and are produced by one of two basic methods–the bromination of polystyrene or the polymerization of bromostyrene monomers.

In general, the materials made by the two production methods are not equivalent. For example, bromination of polystyrene will result in undesirable side chain halogenation, causing a reduction in thermal stability or requiring expensive treatment to remove the more labile bromine atoms. Polymers prepared by the polymerization of bromostyrene do not have undesirable side chain halogenation, and are preferred for their relatively greater thermal stability.

Not only do the two methods of preparing brominated polystyrenes provide different end products, there are also numerous disadvantages inherent to the bromination of polystyrene approach. First, such methods require that the polymer be solubilized, necessitating isolation and purification procedures that may add significantly to production costs. Also, because the product is recovered from solution, the final product will be a dusty powder unless some type of compaction step is included at additional cost. Similarly, unless a post-production compounding step is used, the introduction of co-additives is limited to dry blending with other powders.

A more significant disadvantage of the bromination of polystyrene method is that the brominated polystyrenes produced are limited to copolymer compositions and molecular weights that are readily available. In addition, the products must be structures that are stable to, and will not interfere with, the bromination process.

The polymerization of bromostyrene has several advantages over the bromination of polystyrene. As mentioned, it provides a more thermally stable product because side chain halogenation is avoided. Also, this method can be used to produce a continuum of molecular weights and bromine contents not otherwise available. Further, the polymerization can be accomplished without the use of solvents, and is readily adaptable to more economical continuous production processes. In addition, a broad spectrum of copolymer compositions may be produced simply by adjusting the monomer feed. Finally, production of convenient non-dusting pellets (with the option of incorporating auxiliary additives) is a natural by-product of the inventive polymerization process, and may be provided at no additional cost.

Nowhere in the literature of bromostyrene polymers is there any indication that the practical bulk polymerization of these monomers to produce a highly brominated compositions has been addressed. One reason for this omission may be the lack of thermal stability of the brominated materials. Conditions that would normally be used to prepare commercial polystyrene (such as flash devolatilization at temperatures approaching 300.degree. C.) would cause thermal breakdown of most brominated materials, and product discoloration and equipment corrosion would result. Processes using solution and emulsion techniques avoid any possibility of decomposition, even though they are at an economic disadvantage.

A need therefore exists for improved methods of continuously polymerizing bromostyrenes. In particular, a need exists for a method of polymerizing bromostyrenes without the need of solvents and their associated disadvantages. A need also exists for a method of polymerizing bromostyrenes in which the reaction is run to a high degree of completion in a relatively brief period of time. The present invention addresses these needs.

SUMMARY OF THE INVENTION

Briefly describing one aspect of the present invention, there is provided a process for the solventless polymerization of brominated styrenes, comprising the steps of: (a) blending monomers of brominated styrenes with a polymerization initiator; (b) feeding the monomer/polymerization initiator mix into a prepolymerizer wherein the monomers begin to polymerize; and (c) feeding the monomer/polymerization initiator mix and the partially polymerized bromostyrene into a screw-type extruder to drive the polymerization to a high degree of completion in a short period of time. Optionally, the monomers may be preheated before mixing with the initiator, or a heater may be included in the prepolymerizer. Also, a second initiator may be used to facilitate polymerization in the extruder reaction zone.

One object of the present invention is to provide a continuous process for producing brominated styrene homo- and copolymers, wherein the process uses an extruder for at least a portion of the polymerizations.

A further object of the present invention is to provide a screw-type extruder effective for providing a high degree of conversion from monomer to polymer while maintaining an unexpectedly high molecular weight.

A further object of the present invention is to provide an improvement to the basic polymerization process in which the early stages of the polymerization are carried out in a prepolymerizer which may optionally be preceded by a preheater.

It is also an object of the present invention to provide an improved polymerization process in which the free radical source for the prepolymerizer is selected so as to provide rapid initiation at temperatures below 100.degree. C.

Another object of the present invention is to provide an improved polymerization process in which desired additives may be introduced continuously into the brominated polymer during polymerization, thereby avoiding the expense of a separate compounding step.

An additional object of the present invention is to provide polymers that contain about 50% or more by weight of brominated styrene and that are useful as flame retardant additives.

A further object of the present invention is to provide a flame retarding polymer comprised predominantly of brominated styrene and having an APHA solution color of less than 500 following heat ageing for eight hours at 243.degree. C. in a test tube.

Additional objects and advantages of the present invention will be apparent from the following description of preferred embodiments.
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Dr. Enrico J. Termine is a senior executive and scientist with thirty years of experience in business leadership, research & development, product engineering, marketing, and manufacturing. He has consulted for a variety of industrial and legal clients on engagements involving valuations, due diligence assignments, market research reports, strategy development reports, science and technology assessments, and root cause investigations. Dr. Termine is a bromine chemistry expert. He specializes in oilfield applications, flame retardant plastics, industrial and recreational water treatment and disinfection, specialty and fine chemicals, polymer additives, plastics, and organic synthesis for life science molecules and advanced materials. Dr. Termine earned both his Bachelor of Science in Chemistry and his Ph.D. in Organic Chemistry from the University of Miami. He has collaborated on more than 38 patents and publications. His technical contributions are useful in consumer electronics; for petroleum and petrochemical processing; in transportation and industrial products; in healthcare; for industrial and household disinfection; and in building and construction materials.

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