# Patent

## Title
Low molecular weight brominated polymers and their use in thermoplastic formulations

## Abstract

This invention relates flame retardant compositions containing low molecular weight brominated anionic, chain transfer, vinyl aromatic polymers, hereinafter “ACTVAP”. The compositions can accommodate high bromine content while still exhibiting a low thermally labile bromine content. The compositions have glass transition temperatures, Tg, that are predictive of acceptable melt flows and heat distortion temperatures (HDT) in HIPS and ABS based formulations substrates. The compositions, are suitable flame retardant candidates for use in thermoplastic formulations, e.g. polystyrene and ABS formulations.

## Background
REFERENCE TO RELATED APPLICATIONS
This application is the National Stage of International Patent Appl. No. PCT/US2008/066218, filed on Jun. 6, 2008, which in turn claims the benefit of U.S. Provisional Patent Appl. No. 60/942,599, filed on Jun. 7, 2007, the disclosures of which are incorporated herein by reference.


TECHNICAL FIELD
This invention relates to flame retardant compositions containing brominated anionic, chain transfer, vinyl aromatic polymers, hereinafter brominated “ACTVAP”. The compositions can accommodate high bromine content while still exhibiting a low thermally labile bromine content. The compositions have glass transition temperatures, Tg that are predictive of acceptable melt flows in high impact polystyrene (HIPS) and acrylonitrile-butadiene-styrene (ABS) based formulations. Articles produced from such formulations have good heat distortion temperatures. The compositions, are suitable flame retardant candidates for use in thermoplastic formulations, e.g. HIPS and ABS formulations.
BACKGROUND
Brominated polystyrenic (styrenic polymer) compositions have long been used as flame retardants in thermoplastic formulations. Brominated polystyrenes can be produced by bromination of polystyrenes, the polystyrenes being derived by free-radical or anionic polymerization of styrenic monomer, see for example, commonly-owned U.S. Pat. Nos. 5,677,390, 5,686,538, 5,767,203, 5,852,131, 5,852,132, 5,916,978, 6,133,381, 6,207,765, 6,232,393, 6,232,408, 6,235,831, 6,235,844, 6,326,439, and 6,521,714.
While the forgoing compositions have and are meeting considerable commercial success, the skilled artisan is always searching for the next generation product that shows commercial promise.
SUMMARY OF THE INVENTION
This invention relates to flame retardant compositions comprising a brominated anionic, chain transfer, vinyl aromatic polymer (ACTVAP), wherein the compositions: (i) contain at least about 72 wt % bromine; and (ii) contain less than about 1,000 ppm (weight/weight) thermally labile Br, the wt % and ppm values being based upon the total weight of the composition. Within the invention scope are compositions in which the brominated ACTVAP is brominated anionic, chain transfer styrene polymer (ACTSP).
ACTVAP and ACTSP, as used herein, are acronyms for, in the first case, vinyl aromatic polymer, and, in the second case, styrene polymer that have been anionically derived and that have had their respective chain length distributions determined by a chain transfer mechanism. These polymers are subsequently brominated to yield the flame retardant compositions of this invention. The chain transfer agent is preferably toluene.
The use of the chain transfer mechanism allows for the use of catalytic amounts of conventional alkyl lithium polymerization initiators. The alkyl lithium initiators are also widely used in conventional polymerization of styrene. However, there, the polymer growth is not determined by chain transfer, but rather, by quenching of the lithium end-group, thus requiring the use of stoichiometric amounts (rather than catalytic amounts) of lithium alkyls to obtain the desired polymeric chain lengths. Thus, polymers using a chain transfer mechanism to determine chain length enjoy a considerable cost advantage that inures to the cost advantage of the compositions of this invention.
The flame retardant compositions of this invention exhibit, amongst other things, a glass transition temperature, i.e. Tg that predicts that the use of such compositions to flame retard HIPS and ABS formulations will not frustrate molding qualities and that molded articles produced from such formulations will have acceptable heat distortion temperatures (HDT).
The combination of a favorable Tg combined with a high bromine content and a low thermally labile bromine content provides a particularly preferred flame retardant composition of this invention.
The higher bromine content means that the flame retardant compositions of this invention can deliver more bromine, and hence more flame retardancy, to a HIPS or ABS formulation than the same weight of a composition having a lower bromine content. That quality offers cost savings opportunities for the manufacturer of the final thermoplastic article.
Low thermally labile bromine contents are desired since formulation compounding and article manufacturing conditions tend to release thermally labile bromine as HBr, which gas can be destructive of compounding and molding equipment.
In regard to bromine in the HIPS or ABS formulation or articles formed therefrom, it is mentioned that the compositions of this invention are essentially free (less than 50 ppm), if not totally free, of occluded bromine. Occluded bromine is bromine captured in the flame retardant composition as Br2. Significant quantities of such bromine are not desirable for obvious reasons.
The flame retardant compositions of this invention have a thermogravimetric analysis (TGA) profile that predicts that the compositions are thermally stable enough to not excessively degrade under compounding and molding conditions but will degrade sufficiently to release their bromine substituent at the much higher temperatures experienced at a “flame front.” The term “flame front” relates to the proximity of a fire to the flame retarded HIPS or ABS article. The fire can be just adjacent the article or emanating from the article itself.
The flame retardant compositions of this invention have good color. They are water-white or at least near water-white when tested by the Hunter Solution Color Value Test, see the “Analytical Methods” section below. In addition, the compositions have excellent YI values when tested in accordance with ASTM D1925. Such YI values are associated with the composition having a white or near white color when color tested as a solid.
The brominated ACTVAP or ACTSP found in the compositions of this invention are derived by the bromination of the corresponding ACTVAP or ACTSP. The unbrominated ACTVAP or ACTSP, can also be referred to as precursor or base ACTVAP or ACTSP. The base ACTVAP or ACTSP can have up to about 25 relative GPC area % monoadduct, e.g. 1,3-diarylpropane. When the aryl groups are phenyl groups, 1,3-diphenylpropane is the monoadduct. However, where desired, the base ACTVAP or ACTSP can be altered, prior to bromination, to have a lower monoadduct content. Alteration is usually effected by distillation to reduce the monoadduct content from the base ACTVAP or ACTSP. Such alteration is believed to be desirable as it is theorized, though this invention is not limited to such theory, that the monoadduct tends to brominate quickly and, thus, consume available bromine at a faster rate than that consumed by the higher molecular weight polymer chains making up the base ACTVAP or ACTSP. Such faster bromine consumption is believed to distort the extent and homogeneity of the bromination of the remainder of the higher molecular polymer constituents. Bromination homogeneity concerns the degree of uniformity in the distribution of aryl bromine along the polymer chain. The non-end group aryl groups are usually kinetically slower to brominate and hence harder to highly brominate than the terminal or “end-group” aryl-groups due to steric hindrances resulting from the internal molecular structure.
Disproportionate distribution of the bromine between the brominated monoadduct and the rest of the polymer constituents in the brominated ACTVAP or ACTSP can result in a flame retardant composition with a lower glass transition temperature, Tg, than would otherwise occur. If depressed enough, the lower Tg predicts enhanced molding performance (high melt flow index) for the host HIPS or ABS and a reduced heat distortion temperature (HDT) for articles produced from the flame-retarded HIPS or ABS.
In the following “Detailed Description of the Invention” further description is given for the compositions of this invention. The compositions to which the description applies, in part or in whole, are within the scope of the inventions disclosed herein.
Thermoplastic articles containing any one or more of the compositions of this invention are within the scope of the invention.


DETAILED DESCRIPTION OF THE INVENTION
Compositions of this Invention
Compositions of this invention are predominant in brominated ACTVAP or ACTSP. Generally, the compositions will contain at least about 97 wt % brominated ACTVAP or ACTSP, with the remainder being by-product impurities. Such impurities are, for the most part, by-products of either the polymerization or bromination processes used to ultimately obtain the brominated ACTVAP or ACTSP. Most preferred flame retardant compositions of this invention contain from about 99 to about 99.95+ wt % polymer based on the total weight of the composition.
Base ACTVAP can be represented by the formula:

Ar—CRH[—CH2CH(Ar)]n average—CH2CH2—Ar,

wherein Ar is an aryl group, R is a C1-C4 alkyl group or a hydrogen atom and naverage is the average number of repeating units and is based on the number average molecular weight, Mn, of the ACTVAP distribution. naverage is calculated:

naverage=(Mn−formula wt ArCRH−formula wt ArCH2CH2)/(formula wt ArCH2CH2).

Base ACTSP are those having the structure:

C6H5-CH2[—CH2CH(C6H5)]naverageCH2CH2—C6H5 

wherein the average naverage value is determined by the formula:

naverage=(Mn−196.29)/104.15.

The method of determining the Mn for ACTVAP and ACTSP is described in the “Analytical Methods” section hereof.
The polymerization method for producing base ACTVAP or ACTSP can be generally described as the anionic polymerization of vinyl aromatic/styrene in the presence of toluene solvent (which also participates as the transfer agent) and a catalytic amount of butyllithium that is promoted with N,N,N′,N′-tetramethylethylenediamine (TMEDA). See Examples ACTSP 1-12 herein.
For the reasons discussed previously, the monoadduct content of the base ACTVAP or ACTSP invention is preferred not to exceed about 25 GPC area %. monoadduct, e.g. 1,3-diphenylpropane for ACTSP. (See GPC analysis in the “Analytical Methods section hereof.) Some base ACTVAP or ACTSP of this invention are designed to contain no more than about 10 GPC area % monoadduct, while others are designed to contain no more than about 5 GPC area % monoadduct. Almost monoadduct-free base ACTVAP or ACTSP will contain no more than about 1 GPC area % monoadduct. The compositions of this invention will reflect the amount of monoadduct present in the base ACTVAP or ACTSP with their own brominated monoadduct contents of like GPC area percents. For example, a composition produced from an ACTVAP or ACTSP containing less than about 25 GPC area % will in turn contain less than about 25 GPC area % brominated monadduct, based on the total weight of the composition.
Since the flame retardant compositions of this invention contain at least about 97 wt % brominated ACTVAP or ACTSP, and in preferred cases, 99 or more wt % brominated ACTVAP or ACTSP, the molecular weight measured for the compositions of this invention are considered to be the same as that for the brominated ACTVAP or ACTSP components. When the compositions and the brominated ACTVAP or ACTSP of this invention are subjected to polymeric analysis by GPC (See the “Analytical Methods section herein), an Mw within the range of from about 1,000 to about 21,000 Daltons will be measured, preferred is the range of from about 1,250 to about 14,000 Daltons. The range for the Mn value will be within the range of from about 860 to about 18,500 Daltons, preferred is the range of from about 1070 to about 8,200 Daltons. The polydispersity (Mw/Mn) is below 2.2 and is generally found to be within the range of from about 1.1 and about 1.7.
An important feature of flame retardant compositions of this invention is their compatibility with the host thermoplastic substrate, e.g. HIPS and ABS formulations. Compatibility is evidenced by the relatively small domain size of the compositions of this invention within the articles formed from the host thermoplastic formulation. Compatibility is a function of the degree of miscibility of the compositions in the host thermoplastic substrate. Domain sizes of from about 0.5 to about 2 microns are characteristic of compositions of this invention in formed HIPS or ABS articles. Miscibility is considered to be a function of polymer size and the composition's Tg. Generally, non-polymeric flame-retardants containing high levels of aryl bromine, e.g. >71 wt % bromine, and high molecular weight brominated polymers do not enjoy this compatibility.
Preferred flame retardant compositions of this invention have a Tg within the range of from about 35° C. to about 165° C., and preferably within the range of from about 75° C. to about 135° C. Such Tg values portend good moldability when formulated in HIPS or ABS and good HDT values for products molded from such formulations. If the Tg value is too high, the molding qualities of the formulation will exhibit too low of a melt flow, whereas if the Tg is too low, HDT values for the final molded article can be unacceptably low. The glass transition temperature analysis is described in the “Analytical Methods” section herein.
The flame retardant compositions of this invention contain at least about 65 wt % bromine as determined by analysis of the flame retardant composition by X-Ray Fluorescence analysis (See the “Analytical Methods” section herein). Since the brominated ACTVAP or ACTSP components of the compositions of this invention are produced from very robust and well designed base ACTVAP or ACTSP it is possible to apply bromination process conditions that will push the bromine content of these polymers to very high levels without attendant excessive thermally labile bromine production, and excessive chain degradation. Flame retardant compositions of this invention contain from about 65 wt % to about 80 wt % bromine. It is believed that a particularly commercially attractive range will be from about 70 wt % to about 79 wt % bromine. Bromine contents of from about 72 wt % to about 78 wt % bromine are believed to be most favored from a commercial standpoint. The high bromine contents for the flame retardant compositions of this invention should enable lower flame retardant loadings on a weight basis without sacrifice of the flame retarding bromine content of the HIPS or ABS end-product. The forgoing wt % bromine values are based on the total weight of the flame retardant composition.
The flame retardant compositions of this invention, will average from about 2 to about 4.8 bromine substituents per aryl group in the polymer distribution. Preferably, they will average from about 3 to about 4.6 bromine substituents per aryl group in the polymer distribution. Thus, each aryl group in the polymer distribution may contain from about 2 to about 5 bromine substituents per aryl group (on an individual not average aryl group basis). The term “polymer distribution” means the total polymer constituents as measured by GPC analysis of the flame retardant composition and includes any brominated monoadducts present as a polymer constituent of the distribution. It does not include residual chain transfer agent or styrene monomer if present. As mentioned previously, since the compositions of this invention are very high in brominated ACTVAP or ACTSP, the number of bromine constituents in the compositions of this invention is essentially the same as for the brominated ACTVAP or ACTSP. The average number of bromine substituents is calculated by a combination of wt % bromine via XRF and GPC measurement for Mn. The calculation is illustrated as follows:
For 1 mole of material with the formula,

C6H(5-x)BrxCH2(C6H(5-x)BrxCHCH2-)naverageCH2CH2—C6H(5-x)Brx 

where x is the average number of bromine atoms per phenyl group. then,

x=Brmoles/Phenylaverage 

Total moles of Bromine (Brmoles) is given by:

Brmoles=(Mn(brominated))·(wt % Br/80)

The average number of phenyl rings in one mole (Phenylaverage) is given by

Phenylaverage=2+naverage 

where:

naverage=(Mn(unbrominated)−196.29)/104.15

and:

Mn(unbrominated)=Mn(brominated)·(1−wt % Br/100),

therefore x is given by

x=Brmoles/Phenylaverage=Mn(brominated)·(wt % Br/80)/2+naverage 

x=Mn(brominated)·(wt % Br/80)/(2+[(Mn(unbrominated)−196.29)/104.15])

x=Mn(brominated)·(wt % Br/80)/(2+[Mn(brominated)·(1−wt % Br/100)−196.29)/104.15])

The x values are given for each of the Brominated Examples in Table I.

The wt % bromine is affected by selection of the process parameters for the bromination of the base ACTVAP or ACTSP. Parameters, such as, bromination time, catalyst used, catalyst amount, reaction solvent, reaction temperature and the amount of bromine present, can influence the amount of bromination obtained. (See Bromination Examples 1-30)
Despite the relatively high bromine contents of the flame retardant compositions of this invention, it is a feature of such compositions that they exhibit relatively low thermally labile bromine contents.
The amount of thermally labile bromine in the compositions of this invention is low and falls within the range of from the detectable limits of the test to about 1000 ppm (weight/weight and based on the total weight of the composition) as measured at 300° C. for 15 minutes in accordance with the method described in the “Analytical Methods” section hereof. Thermally labile bromine contents may also fall within the narrower ranges of from the detectable limits of the test to about 750 ppm and from the detectable limits of the test to about 500 ppm. See Bromination Examples 1-30. The detectable limits of the test are evidenced by unacceptable loss of precision, usually occurring when attempting to measure thermally labile bromine in amounts less than 50 ppm. It is to be understood that flame retardant compositions of this invention can contain thermally labile bromine amounts lower than about 50 ppm when determined by tests that are capable of precision and accuracy at these low concentrations.
Besides having low thermally labile bromine contents, compositions of this invention must be otherwise thermally stable. They must be thermally stable so they do not degrade during the molding or compounding processes. They also must be stable under expected conditions of use, transport and storage. But the composition cannot be overly stable since to function as a flame retardant in the host HIPS or ABS substrate, the brominated ACTVAP or ACTSP constituent needs to thermally degrade only in the face of a fire threat. It is a feature of aryl bromine that, when in admixture with a flame retardant synergist, it does degrade and release its flame retarding bromine at a temperature, which is closely aligned with the temperatures that would be expected at a “flame front.” Such release allows the bromine to interfere with the flame chemistry and thereby function as a flame retardant.
The flame retardant industry considers Thermal Gravimetric Analysis (TGA) to be an indicator of how a candidate flame retardant will perform in actual use. Compositions of this invention have a TGA 5 wt % loss, under nitrogen, at a temperature within the range of from about 290° C. to about 380° C. It is expected that the flame retardant industry will prefer a TGA 5 wt % loss under nitrogen at a temperature within the range of from about 300° C. to about 370° C. Refer to the “Analytical Methods” section herein for a description of TGA analysis
Compositions of this invention, as before said have good color. As measured by the Hunter Solution Color Value Test described in the “Analytical Methods” section hereof, the composition obtains Delta E values within the range of from about 0.4 to about 17. When the color is measured for the solid composition in accordance with ASTM D1925, YI values within the range of from about 1 to about 8 are obtained. Preferred YI values are within the range of from about 1 to about 6.
It is within the scope of this invention that the compositions of this invention can be used in admixture with other flame retardants, e.g. halogenated non-vinyl aromatic flame retardants, e.g. decabromodiphenylethane, decabromodiphenylether and tetrabromobisphenol-A, provided that such other flame retardants and their amounts do not frustrate the obtainment of the desired composition characteristics.
It is to be understood that since most of the compositions of this invention are comprised of at least 97 wt % brominated ACTVAP or ACTSP, when quantitative or qualitative values are recited for compositions of this invention, such values are considered to also apply to the brominated ACTVAP or ACTSP itself when applicable, e.g. Tg, bromine wt % content, thermally labile bromine wt % content, TGA, color, molecular weights, etc.
Thermoplastic Formulations of this Invention
The flame retardant compositions of this invention can be used in thermoplastic formulations based on HIPS or ABS. HIPS and ABS are well known to the art and are commercially available from several sources.
Preferably the compositions of this invention are used as additive flame retardants and are formulated with the HIPS or ABS based formulation in an amount sufficient to obtain the level of flame retardancy sought, generally a UL 94 rating of V-0 or V-2 for 1⁄8 inch test strips produced from the formulation. The formulation can comprise, and probably will comprise, other conventional additives. Conventional additives, such as flame retardant synergists, antioxidants, UV stabilizers, drip suppressants, pigments, impact modifiers, fillers, acid scavengers, blowing agents, and the like, can be included selected and used in suitable amounts in the formulations as is appropriate to achieve the function that each additive is to perform. Such selection and amounts are within the routine skill of the artisan. Preferred HIPS and ABS based formulations of this invention contain a flame retardant synergist.
Flame retarded HIPS and ABS based formulations contain within the range of from about 3 to about 25 wt % flame retardant compositions of this invention, the wt % being based on the total weight of the formulation. Preferred amounts are within the range of from about 5 to about 15 wt %.
The flame retardant compositions of this invention are used with flame retarding synergist. These synergists are those that are commonly used with aryl brominated flame retardants and are well know in the art. Exemplary of such synergists are iron oxide, zinc borate, or, preferably, antimony oxide synergist, such as, antimony trioxide, antimony pentoxide, potassium antimonite, sodium antimonite. The amount of flame retardant synergist, when used, generally will be in the range of up to about 12 wt % based on the total weight of the HIPS or ABS based formulation. Synergist amounts will most often fall within the range of from about 1 to about 6 wt %. Departures from the foregoing ranges of proportions are permissible whenever deemed necessary or desirable under the particular circumstances at hand, and such departures are within the scope and contemplation of this invention.
This invention includes masterbatch compositions in which flame retardant compositions of this invention are blended with conventional amounts of common additives and with HIPS or ABS in a weight ratio (HIPS or ABS: composition of the invention) in the range of, say, 1:99 to 70:30. Such masterbatch formulations need not, but may also contain at least one flame retardant synergist such as iron oxide, zinc borate, or preferably an antimony oxide flame retardant synergist such as antimony trioxide, antimony pentoxide, potassium antimonite, sodium antimonite. The thus formed masterbatches are suitable to be “let down” in HIPS or ABS to form the finished formulation.
Various known procedures can be used to prepare the blends or formulations described herein. For example the HIPS or ABS, the flame retardant composition of this invention and any other components or ingredients to be used in the finished formulation can be blended together in powder form and thereafter molded by extrusion, compression, or injection molding. Likewise the components can be mixed together in a Banbury mixer, a Brabender mixer, a roll mill, a kneader, or other similar mixing device, and then formed into the desired form or configuration such as by extrusion followed by comminution into granules or pellets, or by other known methods.
Preferred flame retarded HIPS or ABS formulations described herein or those that have the capability of forming molded specimens of 3.2 millimeter thickness (1⁄8-inch thickness) that pass at least the UL 94 V0 test. Less preferred, but still having commercial utility, are those HIPS or ABS formulations having the capability of forming molded specimens 1.6 millimeter ( 1/16-inch) thick that obtain a UL 94 V2 rating.
ANALYTICAL METHODS
Known analytical methods can be used or adapted for use in assaying the characteristics of the compositions and formulations of this invention.
Total Bromine Content.
Since the compositions of this invention have good, or at least satisfactory, solubility in solvents such as tetrahydrofuran (THF), the determination of the total bromine content for the compositions of this invention is easily accomplished by using conventional X-Ray Fluorescence techniques. The sample analyzed is a dilute sample, say 0.1 g+/−0.05 g in 60 mL THF. The XRF spectrometer can be a Phillips PW1480 Spectrometer. A standardized solution of bromobenzene in THF is used as the calibration standard. The total bromine values described herein and reported in the Examples are all based on the XRF analytical method.
Hunter Solution Color Value Test.
To determine the color attributes of the flame retardant compositions of this invention, use is again made of the ability to dissolve these compositions in easy-to-obtain solvents, such as chlorobenzene. The analytical method used is quite straight-forward. Weigh 5 g+/−0.1 g of the composition into a 50 mL centrifuge tube. To the tube also add 45 g+/−0.1 g chlorobenzene. Close the tube and shake for 1 hour on a wrist action shaker. After the 1 hour shaking period, examine the solution for undissolved solids. If a haze is present, centrifuge the solution for 10 minutes at 4000 rpm. If the solution is still not clear, centrifuge an additional 10 minutes. Should the solution remain hazy, then it should be discarded as being incapable of accurate measurement. If, however, and this is the case most of the time, a clear solution is obtained, it is submitted for testing in a HunterLab Color Quest Sphere Spectrocolorimeter. A transmission cell having a 20-mm transmission length is used. The colorimeter is set to “Delta E-lab” to report color as ΔE and to give color values for “L”, “a” and “b”. Product color is determined as total color difference (ΔE) using Hunter L, a, and b scales for the 10% by weight concentrations of the product in chlorobenzene versus chlorobenzene.
Yellowness Index Hunter Colorimeter
Compositions of this invention were subjected to the analysis described in ASTM D1925
Tg Values
Tg values were obtained by DSC with a TA Instruments DSC Model 2920. Samples were heated to 400° C. at a rate of 10° C./min under nitrogen. Tg is determined by noting the change in the specific heat of a polymer at the glass to rubber transition. This is a second order endothermic transition (requires heat to go through the transition). In DSC, the transition appears as a step transition and not a peak such as might be seen with a melting transition. See, The Elements of Polymer Science and Engineering, An introductory Text for Engineers and Chemist, Alfred Rudin, Academic Press, Orlando Fla., 1982, pg 403.
Thermogravimetric Analysis.
Thermogravimetric analysis (TGA) is also used to test the thermal behavior of the flame retardant compositions of this invention. The TGA values are obtained by use of a TA Instruments Thermogravimetric Analyzer. Each sample is heated on a Pt pan from 25° C. to about 600° C. at 10° C./min with a nitrogen flow of 50-60 mL/min.
Thermal Stability Test (Thermally Labile Bromine Test).
This test procedure essentially as described in U.S. Pat. No. 5,637,650. In conducting this test, each sample is run in duplicate. A 2.00 g+/−0.01 g sample is placed into a new clean 20 mm by 150 mm test tube. With a neoprene stopper and Viton® fluoroelastomer tubing, the test tube is connected to a nitrogen purge line with exit gas from the test tube being passed successively through subsurface gas dispersion frits in three 250-mL sidearm filter flasks each containing 200 mL of 0.1 N NaOH and 5 drops of phenolphthalein. With a constant nitrogen purge at 0.5 SCFH, the test tube is heated at 300° C. in a molten salt bath (51.3% KNO3/48.7% NaNO3) for 15 minutes followed by 5 minutes at ambient temperature. The test tube containing the sample is then replaced with a clean dry test tube, and the apparatus is purged with nitrogen for an additional 10 minutes with the empty test tube in the 300° C. salt bath. The test tube, tubing and gas dispersion tubes are all rinsed with deionized water, and the rinse is combined quantitatively with the solutions in the three collection flasks. The combined solution is acidified with 1:1 HNO3 and titrated with 0.01 N AgNO3 using an automatic potentiometric titrator (Metrohm 670, 716, 736, or equivalent). Results are calculated as ppm HBr ppm: HBr=(mL AgNO3 to end point)·(normality of AgNO3) (80912)/(sample wt.). The tubing is thoroughly dried with nitrogen before the next analysis. Each day before the first sample, three empty clean test tubes are run as blanks to assure there is no residual hydrogen halide in the system.
GPC Molecular Weights for Brominated ACTVAP/ACTSP
The Mw, Mn, Mz, Mp and PD values were obtained by GPC using a Waters model 510 HPLC pump and, as detectors, a Waters Refractive Index Detector, Model 410 and a Precision Detector Light Scattering Detector, Model PD2000. The columns were Waters, [mu]Styragel, 500 Å, 10,000 Å and 100,000 Å. The auto-sampler was a Shimadzu, Model Sil 9A. A polystyrene standard (Mw=185,000) was routinely used to verify the accuracy of the light scattering data. The solvent used was tetrahydrofuran, HPLC grade. Based on isolated 1,3diphenylpropane and 1,3,5-triphenylpentane adducts, and the mode of separation is size exclusion, peaks are identified according to their order of elution as 1,3-diphenylpropane, 1,3,5-triphenylpentaned, 1,3,5,7-tetraphenylheptaned, 1,3,5,7,9-pentaphenylnonane, etc. The individual peaks of the oligomeric material are then assigned theoretical molecular weight values. A calibration curve is constructed using these theoretical values and their corresponding retention times. Based on this calibration, the overall distribution data is calculated and reported. The test procedure used entailed dissolving 0.015 g-0.020 g of sample in 10 mL of THF. An aliquot of this solution is filtered and 50 L is injected on the columns. The separation was analyzed using software provided by Precision Detectors for the PD 2000 Light Scattering Detector.
GPC Molecular Weights for Base ACTVAP and ACTSP
The Mw, Mn, Mp, Mz and PD values were obtained by GPC using a modular system with a Shimadzu autosampler (model SIL-9), a Shimadzu refractive index detector (model RID-6A), a Waters HPLC pump (model 510) and a Waters TCM column heater. The columns were Polymer Labs (Varian) Oligopore columns, 300 mm by 7.5 mm, part number 1113-6520, or equivalent. The solvent used was tetrahydrofuran, HPLC grade. The test procedure used entailed dissolving 0.10 g of sample in 10 mL of THF. An aliquot of this solution is filtered and 50 μL is injected on the columns. The calculations were performed by the Viscotek Omnisec, version 4.2.0.237 (or equivalent) gel permeation chromatography (GPC) data collection and processing system.
Analytical Methods for Molding Articles:
HDT was determined by ASTM D 648; Vicat, ° C. by ASTM D 649; Izod Impact by ASTM D 256; Melt Flow Index by ASTM D 1238; and UL-94, 1⁄8′′ (32 mm) rating by UL 94.
The following Examples illustrate principles of this invention and are not intended to limit the generic scope of this invention.
EXAMPLES
ACTSP Examples 1-10
General: A spherical glass 12 liter creased reactor with oil jacket was equipped with a reflux condenser, distillation head, submerged thermal couple, bottom drain valve, and stainless steel internal cooling coils. Temperature was tightly maintained at a set point via PID controller that regulates water flow to the cooling coils. Vigorous agitation was accomplished by means of a overhead stirring assembly comprised of 19 mm OD glass shaft with two sets of glass impellers, one set pitched and the other flat, fused to the shaft. The reactor was essentially free of all wetted PTFE parts or other polymeric fluorinated materials or elastomers.
In all examples the reactor was maintained under an inert dry N2 atmosphere during all operations. The reactor was charged with the chain transfer agent(s) through a dip leg by means of a diaphragm pump. Alkyl lithium, metal alkoxides (when used), additional solvents and the amine promoter (TMEDA) were all fed subsurface to the stirred chain transfer agent(s) in that order through the same dip leg. Styrene was pumped into the reactor by means of a metering pump through a 3′′ (76.2 mm) cylindrical column (1.75′′ (44.45 mm) dia.≈100 g) of Basic Aluminum Oxide (EMD Chemicals, Aluminum oxide 90, mesh 70-230, column chromatography grade) and delivered as a fine stream or spray above the surface of the reaction mixture through two 1/16′′ (16 mm) OD feed nozzles.
Example 1
ACTSP-1 Mw=483 PD=1.32
Toluene, 4323 g (5.0 liters, 46.92 mol) was charged to the reactor previously heated to 70° C. by means of the hot oil jacket. The PID controller operating the cooling coils was set for 70° C. As the content of the reactor was heated to the reaction temperature, 63.94 g n-BuLi solution (2M in cyclohexane, 0.165 mol) was charged through the dip leg below the surface of the gently agitated (300 rpm) toluene reaction mixture. The feed line was then flushed with 75 ml of anhydrous toluene. Next a previously prepared solution comprised of potassium t-butoxide (18.28 g, 0.163 mol), TMEDA (94.26 g, 0.811 mol), and toluene (421.27 g, 4.7 mol) was introduced forming a characteristic bright red color of a TMEDA complexed benzyl anion with concomitant off gassing of butane. The subsurface line was flushed with a second 75 ml aliquot of anhydrous toluene via metering pump. An additional 350 ml of anhydrous toluene was fed at a constant rate during the anionic chain transfer polymerization process. Reactor agitation was increased to 510 rpm and 2523 g of styrene (99+%, 24.22 mol) were fed over 150 minutes. The well-calibrated metering pump was programmed to feed at a constant rate of 16.82 g/min. Anhydrous cyclohexane (2×200 ml) was charged to the styrene feed system to flush the alumina bed and complete the styrene feed. The styrene feed to the reactor was deemed complete when no further heat of reaction was observed, generally signified by the automated closing of the solenoid valve on the reactor's cooling coils.
The reaction mixture was quenched at 70° C. with a 50 ml aliquot of deoxygenated water resulting in a water white turbid mixture. The reaction mixture was washed with deoxygenated water (3×650 ml) phase cuts could be made after some settling time. Water and any rag or emulsion was removed through the bottom drain valve.
The temperature of the oil jacket was increased to 130° C. while the control valve to the cooling coils was turned off. Residual moisture was removed over a period of approximately two hours as the pot temperature climbed from 65° C. to 115° C.; while water, cyclohexane and some toluene were distilled. An analytical sample was removed, GPC analysis provided the following data: Mp: 197, Mn: 331, Mw: 368, Mz: 406, PD: 1.11.
The crude reaction mixture, 7027 g, was stripped in a continuous operation of excess toluene to yield 3231 g of the concentrated product stream that had the following GPC analysis: Mp: 300, Mn: 367, Mw: 483, Mz: 634, PD: 1.32. The continuous strip was accomplished by means of wiped film evaporator (WFE, aka. Pope Still). WFE operating conditions: feed rate=1.33 L/hr, oil jacket temperature=185° C., Pressure=50 mm Hg and condenser temperature=0° C. An additional 440 g of toluene was collected in a dry ice trap, while the cold finger condensed 3280 g of a mixture of toluene and 1,3-diphenylpropane free of structural isomers.
Example 2
ACTSP-2 Mw=496 PD=1.32
Toluene, 4763 g (5.5 liters, 51.69 mol) was charged to the reactor previously heated to 80° C. by means of the hot oil jacket. The PID controller operating the cooling coils was set for 80° C. As the solvent was heated to the reaction temperature, 111.65 g n-BuLi solution (2M in cyclohexane, 0.288 mol) was charged through the dip leg below the surface of the gently agitated (300 rpm) toluene reaction mixture. The feed line was then flushed with 75 ml of anhydrous toluene. Once the pot temperature reached 80° C., 49.46 g of N,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.426 mol) was charged to the reactor through the subsurface feed line forming the characteristic bright red color of TMEDA complexed benzyl lithium anion with concomitant off gassing of butane. The subsurface line was flushed with a second 75 ml aliquot of anhydrous toluene via metering pump. An additional 350 ml of anhydrous toluene was fed at a constant rate during the anionic chain transfer polymerization process. Reactor agitation was increased to 510 rpm and 2951 g of styrene (99+%, 28.33 mol) were fed over 180 minutes. The well-calibrated metering pump was programmed to feed at a constant rate of 16.4 g/min. Anhydrous cyclohexane (2×200 ml) was charged to the styrene feed system to flush the alumina bed. The styrene feed to the reactor was deemed complete when no further heat of reaction was observed generally signified by the closing of the automated control valve on the cooling coils.
The PID temperature controller was left at 80° C. and water was fed through the cooling coils while the flow of the hot oil was altered to bypass the reactor jacket. The reaction mixture was quenched at 80° C. with a 50 ml aliquot of deoxygenated water resulting in a water white turbid mixture. The reaction mixture was washed with deoxygenated water (3×650 ml). Phase cuts were rapid and required little settling time. Water and any rag or emulsion was removed through the bottom drain valve.
The temperature of the oil jacket was increased to 130° C. while the control valve to the cooling coils was turned off. Cyclohexane, residual moisture and toluene were distilled through a simple distillation head (1 atm.) until a pot temperature of 115° C. was observed. An aliquot was removed for analysis via GPC (Mp: 195, Mn: 300, Mw: 416, Mz: 624, PD: 1.38)
The crude reaction mixture, 804 g, was stripped via continuous operation of excess toluene to yield 4011 g of an intermediate product stream that had the following GPC analysis: Mr: 191, Mn: 314, Mw: 426, Mz: 615, PD: 1.40. The continuous strip was accomplished by means of wiped film evaporator (WFE, aka. Pope Still). WFE operating conditions were as follows: feed rate=1.33 L/hr, oil jacket temperature=190° C., Pressure=55 mm Hg and condenser temperature=0° C. An additional 918 g of toluene was collected in a dry ice trap, while the cold finger condensed 2942 g of a mixture of toluene and 1,3-diphenylpropane.
A second pass of the 855.4 g of the concentrate through the WFE produced 698 g of an oligomeric mixture with the following GPC profile: Mr: 298, Mn: 375, Mw: 496, Mz: 715, PD: 1.32. WFE operating conditions were as follows: feed rate=1.33 L/hr, oil jacket temperature=200° C., Pressure=10 mm Hg and condenser temperature=0° C. A mixture (155 g) of 1,3-Diphenylpropane and traces of its structural isomers (methylated diphenylethanes) were collected as a distillate.
Example 3
ACTSP-3 Mw=530 PD=1.47
Toluene, 4758 g (5.5 liters, 51.64 mol) was charged to the reactor previously heated to 90° C. by means of the hot oil jacket. The PID controller operating the cooling coils was set for 90° C. As the solvent was heated to the reaction temperature, 73.37 g n-BuLi solution (2M in cyclohexane, 0.189 mol) was charged through the dip leg below the surface of the gently agitated (300 rpm) toluene reaction mixture. The feed line was then flushed with 75 ml of anhydrous toluene. Once the pot temperature reached 90° C., 32.72 g of N,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.282 mol) was charged to the reactor through the subsurface feed line forming the characteristic bright red color of TMEDA complexed benzyl lithium anion with concomitant off gassing of butane. The subsurface line was flushed with a second 75 ml aliquot of anhydrous toluene via metering pump. An additional 350 ml of anhydrous toluene was fed at a constant rate during the anionic chain transfer polymerization process. Reactor agitation was increased to 510 rpm and 2933 g of styrene (99+%, 28.16 mol) were fed over 150 minutes. The well-calibrated metering pump was programmed to feed at a constant rate of 19.5 g/min. Anhydrous cyclohexane (2×200 ml) was charged to the styrene feed system to flush the alumina bed. The styrene feed to the reactor was deemed complete when no further heat of reaction was observed generally signified by the closing of the automated control valve on the cooling coils.
The PID temperature controller was set at 80° C. and water was fed through the cooling coils while the flow of the hot oil was altered to bypass the reactor jacket. The reaction mixture was quenched at 80° C. with a 50 ml aliquot of deoxygenated water resulting in a water white turbid mixture. The reaction mixture was washed with deoxygenated water (3 times, 650 ml). Phase cuts were rapid and required little settling time. Water and any rag or emulsion was removed through the bottom drain valve.
The temperature of the oil jacket was increased to 130° C. while the control valve to the cooling coils was turned off. Cyclohexane, residual moisture and toluene were distilled through a simple distillation head (1 atm.) until a pot temperature of 115° C. was observed. An aliquot was removed for analysis via GPC (Mp: 196, Mn: 363, Mw: 555, Mz: 977, PD: 1.53)
The crude reaction mixture, 8062 g, was stripped via continuous operation of excess toluene to yield 3837 g of the concentrated product stream that had the following GPC analysis: Mp: 196, Mn: 359, Mw: 530, Mz: 868, PD: 1.47. The continuous strip was accomplished by means of wiped film evaporator (WFE, aka. Pope Still). WFE operating conditions were as follows: feed rate=1.33 L/hr, oil jacket temperature=175° C., Pressure=70 mm Hg and condenser temperature=0° C. An additional 1182 g of toluene was collected in a dry ice trap, while the cold finger condensed 2896 g of a mixture of toluene and 1,3-diphenylpropane.
Example 4
ACTSP-4 Mw=584 PD=1.50
Toluene, 5801 g (6.7 liters, 62.95 mol) was charged to the reactor previously heated to 115° C. by means of the hot oil jacket. The PID controller operating the cooling coils was set for 115° C. As the solvent was heated to near reflux, 78.31 g n-BuLi solution (2M in cyclohexane, 0.202 mol) was charged through the dip leg below the surface of the gently agitated (300 rpm) toluene reaction mixture. The feed line was then flushed with 75 ml of anhydrous toluene. Once the pot temperature reached 110° C., 24.73 g of N,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.213 mol) was charged to the reactor through the subsurface feed line forming the characteristic bright red color of TMEDA complexed benzyl lithium anion with concomitant off gassing of butane. The subsurface line was flushed with a second 75 ml aliquot of anhydrous toluene via metering pump. An additional 350 ml of anhydrous toluene was fed at a constant rate during the anionic chain transfer polymerization process. Reactor agitation was increased to 510 rpm and 2543 g of styrene (99+%, 24.42 mol) were fed over 120 minutes. The well-calibrated metering pump was programmed to feed at a constant rate of 21.2 g/min. Anhydrous cyclohexane (2×200 ml) was charged to the styrene feed system to flush the alumina bed. The styrene feed to the reactor was deemed complete when no further heat of reaction was observed generally signified by the closing of the automated control valve on the cooling coils.
The PID temperature controller was set to 80° C. and water was fed through the cooling coils while the flow of the hot oil was altered to bypass the reactor jacket. The reaction mixture was quenched at 80° C. with a 50 ml aliquot of deoxygenated water resulting in a water white turbid mixture. The reaction mixture was washed with deoxygenated water (3 times, 650 ml). Phase cuts were rapid and required little settling time. Water and any rag or emulsion was removed through the bottom drain valve.
The temperature oil jacket was increased to 130° C. while the control valve to the cooling coils was turned off. Cyclohexane, residual moisture and toluene were distilled through a simple distillation head (1 atm.) until a pot temperature of 115° C. was observed. An aliquot was removed for analysis via GPC (Mr: 185, Mn: 322, Mw: 457, Mz: 648, PD: 1.42)
The crude reaction mixture, 8528 g, was stripped via continuous operation of excess toluene to yield 3253 g of the concentrated product stream that had the following GPC analysis: Mr: 300, Mn: 389, Mw: 584, Mz: 887, PD: 1.50. The continuous strip was accomplished by means of wiped film evaporator (WFE, aka. Pope Still). WFE operating conditions were as follows: feed rate=1.33 L/hr, oil jacket temperature=170° C., Pressure=95 mm Hg and condenser temperature=0° C. An additional 1154 g of toluene was collected in a dry ice trap, while the cold finger condensed 4092 g of a mixture of toluene and 1,3-diphenylpropane.
Example 5
ACTSP-5 Mw=715 PD=1.40
Toluene, 5848 g (6.76 liters, 63.46 mol) was charged to the reactor previously heated to 115° C. by means of the hot oil jacket. The PID controller operating the cooling coils was set for 115° C. As the solvent was heated to near reflux, 78. g n-BuLi solution (2M in cyclohexane, 0.202 mol) was charged through the dip leg below the surface of the gently agitated (300 rpm) toluene reaction mixture. The feed line was then flushed with 75 ml of anhydrous toluene. Once the pot temperature reached 110° C., 24.0 g of N,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.207 mol) was charged to the reactor through the subsurface feed line forming the characteristic bright red color of TMEDA complexed benzyl lithium anion with concomitant off gassing of butane. The subsurface line was flushed with a second 75 ml aliquot of anhydrous toluene via metering pump. An additional 350 ml of anhydrous toluene was fed at a constant rate during the anionic chain transfer polymerization process. Reactor agitation was increased to 510 rpm and 2548 g of styrene (99+%, 24.46 mol) were fed over 110 minutes. The well-calibrated metering pump was programmed to feed at a constant rate of 23.2 g/min. Anhydrous cyclohexane (2×200 ml) was charged to the styrene feed system to flush the alumina bed. The styrene feed to the reactor was deemed complete when no further heat of reaction was observed generally signified by the closing of the automated control valve on the cooling coils.
The PID temperature controller was set to 80° C. and water was fed through the cooling coils while the flow of the hot oil was altered to bypass the reactor jacket. The reaction mixture was quenched at 80° C. with a 50 ml aliquot of deoxygenated water resulting in a water white turbid mixture. The reaction mixture was washed with deoxygenated water (three times, 650 ml). Phase cuts were rapid and required little settling time. Water and any rag or emulsion was removed through the bottom drain valve.
The temperature oil jacket was increased to 130° C. while the control valve to the cooling coils was turned off. Cyclohexane, residual moisture and toluene were distilled through a simple distillation head (1 atm.) until a pot temperature of 115° C. was observed. An aliquot was removed for analysis via GPC (Mr: 194, Mn: 382, Mw: 595, Mz: 998, PD: 1.56)
The crude reaction mixture, 8660 g, was stripped via continuous operation of excess toluene to yield 3217 g of an intermediate product stream that had the following GPC analysis: Mr: 297, Mn: 399, Mw: 613, Mz: 1003, PD: 1.54. The continuous strip was accomplished by means of wiped film evaporator (WFE, aka. Pope Still). WFE operating conditions were as follows: feed rate=1.33 L/hr, oil jacket temperature=165° C., Pressure=90 mm Hg and condenser temperature=0° C. An additional 813 g of toluene was collected in a dry ice trap, while the cold finger condensed 4600 g of a mixture of toluene and 1,3-diphenylpropane.
A second pass of the concentrate through the WFE produced 2453 g of an oligomeric mixture with the following GPC profile: Mr: 400, Mn: 512, Mw: 715, Mz: 1084, PD: 1.4. WFE operating conditions were as follows: feed rate=1.33 L/hr, oil jacket temperature=205° C., Pressure=0.6 mm Hg and condenser temperature=0° C. A mixture (69 g) of 1,3-Diphenylpropane and its structural isomers (methylated diphenylethanes) were collected as a distillate.
Example 6
ACTSP-6 Mw=740 PD=1.66
Toluene, 4758 g (5.5 liters, 51.64 mol) was charged to the reactor previously heated to 80° C. by means of the hot oil jacket. The PID controller operating the cooling coils was set for 80° C. As the solvent was heated to the reaction temperature, 70.2 g n-BuLi solution (2M in cyclohexane, 0.181 mol) was charged through the dip leg below the surface of the gently agitated (300 rpm) toluene reaction mixture. The feed line was then flushed with 75 ml of anhydrous toluene. Once the pot temperature reached 80° C., 32.99 g of N,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.284 mol) was charged to the reactor through the subsurface feed line forming the characteristic bright red color of TMEDA complexed benzyl lithium anion with concomitant off gassing of butane. The subsurface line was flushed with a second 75 ml aliquot of anhydrous toluene via metering pump. An additional 350 ml of anhydrous toluene was fed at a constant rate during the anionic chain transfer polymerization process. Reactor agitation was increased to 510 rpm and 2933 g of styrene (99+%, 28.16 mol) were fed over 180 minutes. The well-calibrated metering pump was programmed to feed at a constant rate of 16.3 g/min. Anhydrous cyclohexane (2×200 ml) was charged to the styrene feed system to flush the alumina bed. The styrene feed to the reactor was deemed complete when no further heat of reaction was observed generally signified by the closing of the automated control valve on the cooling coils.
The PID temperature controller was left at 80° C. and water was fed through the cooling coils while the flow of the hot oil was altered to bypass the reactor jacket. The reaction mixture was quenched at 80° C. with a 50 ml aliquot of deoxygenated water resulting in a water white turbid mixture. The reaction mixture was washed with deoxygenated water (3 times, 650 ml). Phase cuts were rapid and required little settling time. Water and any rag or emulsion was removed through the bottom drain valve.
The temperature oil jacket was increased to 130° C. while the control valve to the cooling coils was turned off. Cyclohexane, residual moisture and toluene were distilled through a simple distillation head (1 atm.) until a pot temperature of 115° C. was observed.
An aliquot was removed for analysis via GPC (Me: 192, Mn: 425, Mw: 727, Mz: 1398, PD: 1.71)
The crude reaction mixture, 7931 g, was stripped via continuous operation of excess toluene to yield 3490 g of the concentrated product stream that had the following GPC analysis: Me: 295, Mn: 446, Mw: 740, Mz: 1357, PD: 1.66. The continuous strip was accomplished by means of wiped film evaporator (WFE, aka. Pope Still). WFE operating conditions were as follows: feed rate=1.33 L/hr, oil jacket temperature=185° C., Pressure=70 mm Hg and condenser temperature=0° C. An additional 917 g of toluene was collected in a dry ice trap, while the cold finger condensed 3340 g of a mixture of toluene and 1,3-diphenylpropane.
Example 7
ACTSP-7 Mw=800 PD=1.39
Toluene 4758 g, (5.5 liters, 51.64 mol) was charged to the reactor previously heated to reflux and azeotropically dried over a 4 hour period; Karl Fisher moisture analysis indicated 15 ppm residual H2O. The dried toluene was cooled to 75° C. with the oil jacket and PID controller operating the cooling coils both set at that temperature. Upon cooling to the set point temperature, 109.3 g n-BuLi solution (2M in cyclohexane, 0.282 mol) was charged through the dip leg below the surface of the gently agitated (300 rpm) toluene reaction mixture. The feed line was then flushed with 75 ml of anhydrous toluene. Next, 48.7 g of N,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.419 mol) was charged to the reactor through the subsurface feed line forming the characteristic bright red color of TMEDA complexed benzyl lithium anion with concomitant off gassing of butane. The subsurface line was flushed with a second 75 ml aliquot of anhydrous toluene via metering pump. Additionally 350 ml of anhydrous toluene was fed at a constant rate during the anionic chain transfer polymerization process. Reactor agitation was increased to 510 rpm and 2940 g of styrene (99+%, 28.23 mol) were fed over 180 minutes. The well-calibrated metering pump was programmed to feed at a constant rate of 16.3 g/min. Anhydrous cyclohexane (2×200 ml) was charged to the styrene feed system to flush the alumina bed. The styrene feed to the reactor was deemed complete when no further heat of reaction was observed generally signified by the closing of the automated control valve on the coiling coils.
The set point of PID temperature controller was maintained at 75° C. and water was fed through the cooling coils as needed while the flow of the hot oil was altered to bypass the reactor jacket. The reaction mixture was quenched at 75° C. with a 50 ml aliquot of deoxygenated water resulting in a water white turbid mixture. The reaction mixture was washed with deoxygenated water (3 times, 650 ml). Phase cuts were rapid and required little settling time. Water and any rag or emulsion was removed through the bottom drain valve.
The temperature of the oil jacket was increased to 130° C. while the control valve to the cooling coils was turned off. Cyclohexane, residual moisture and toluene were distilled through a simple distillation apparatus. An aliquot was removed for analysis via GPC (Mp: 192, Mn: 447, Mw: 713, Mz: 1196, PD: 1.59)
The crude reaction mixture, 8068 g, was stripped via continuous operation of excess toluene to yield 3380 g of an intermediate product stream that had the following GPC analysis: Me: 297, Mn: 476, Mw: 733, Mz: 1191, PD: 1.54. The continuous strip was accomplished by means of wiped film evaporator (WFE, aka. Pope Still). WFE operating conditions were as follows: feed rate=1.33 L/hr, oil jacket temperature=185° C., Pressure=55 mm Hg and condenser temperature=0° C. Additionally 1935 g of toluene was collected in a dry ice trap, while the cold finger condensed 261 g of a mixture of toluene and 1,3-diphenylpropane.
A second pass of the concentrate through the WFE produced 2715 g of an oligomeric mixture with the following GPC profile: Mp: 398, Mn: 577, Mw: 800, Mz: 1186, PD: 1.39. WFE operating conditions were as follows: feed rate=1.33 L/hr, oil jacket temperature=185° C., Pressure=0.1 mm Hg and condenser temperature=0° C. A mixture (388 g) of 1,3-Diphenylpropane and its structural isomers (methylated diphenylethanes) were collected as a distillate.
Example 8
ACTSP-8 Mw=817 PD=1.30
Toluene, 4332 g (5.0 liters, 47.02 mol) was charged to the reactor previously heated to 75° C. by means of the hot oil Jacket. The PID controller operating the cooling coils was set for 70° C. As the content of the reactor was heated to the reaction temperature, 94 g n-BuLi solution (2M in cyclohexane, 0.242 mol) was charged through the dip leg below the surface of the gently agitated (300 rpm) toluene reaction mixture. The feed line was then flushed with 75 ml of anhydrous toluene. Next a previously prepared solution comprised of potassium t-butoxide (27.32 g, 0.243 mol), TMEDA (35.95 g, 0.309 mol), THF (59.93 g, 0.831 mol) and toluene (433.36 g, 4.7 mol) was introduced forming a characteristic bright red color of a TMEDA complexed benzyl anion with concomitant off gassing of butane. The subsurface line was flushed with a second 75 ml aliquot of anhydrous toluene via metering pump. An additional 350 ml of anhydrous toluene was fed at a constant rate during the anionic chain transfer polymerization process. Reactor agitation was increased to 510 rpm and 2528 g of styrene (99+%, 24.27 mol) were fed over 150 minutes. The well-calibrated metering pump was programmed to feed at a constant rate of 16.81 g/min. Anhydrous cyclohexane (2×200 ml) was charged to the styrene feed system to flush the alumina bed and complete the styrene feed. The styrene feed to the reactor was deemed complete when no further heat of reaction was observed, generally signified by the automated closing of the solenoid valve on the reactor's cooling coils.
The reaction mixture was quenched at 70° C. with a 50 ml aliquot of deoxygenated water resulting in a water white turbid mixture. The reaction mixture was washed with deoxygenated water (3 times, 650 ml) phase cuts though not easy could be made after some settling time. Water and any rag or emulsion was removed through the bottom drain valve.
The temperature of the oil jacket was increased to 130° C. while the control valve to the cooling coils was turned off. Residual moisture was removed over a period of approximately two hours as the pot temperature climbed from 65 to 115° C.; water, cyclohexane, THF and toluene taken overhead. An aliquot was removed for analysis via GPC provided the following data: Mp: 405, Mn: 509, Mw: 790, Mz: 1180, PD: 1.55.
The crude reaction mixture, 7215 g, was stripped in a continuous operation of excess toluene to yield 2894 g of an intermediate product stream that had the following GPC analysis: Mp: 402, Mn: 530, Mw: 767, Mz: 1039, PD: 1.45. The continuous strip was accomplished by means of wiped film evaporator (WFE, aka. Pope Still). WFE operating conditions: feed rate=1.33 L/hr, oil jacket temperature=185° C., Pressure=55 mm Hg and condenser temperature=0° C. An additional 1435 g of toluene was collected in a dry ice trap, while the cold finger condensed 2884 g of a mixture of toluene and 1,3-diphenylpropane.
A second pass of the product stream through the WFE produced 2415 g of a oligomeric mixture with the following GPC profile: Mp: 409, Mn: 645, Mw: 817, Mz: 1009, PD: 1.27. WFE operating conditions: feed rate=1.33 L/hr, oil jacket temperature=185° C., Pressure=0.1 mm Hg and condenser temperature=0° C. 271 g of 1,3-diphenylpropane free of structural isomers was collected as a distillate.
Example 9
ACTSP-9 Mw=928 PD=1.43
Toluene 4758 g, (5.5 liters, 51.64 mol) was charged to the reactor previously heated to reflux and azeotropically dried over a 4 hour period; Karl Fisher moisture analysis indicated 16 ppm residual H2O. The dried toluene was cooled to 80° C. with the oil jacket and PID controller operating the cooling coils both set at that temperature. Upon cooling to the set point temperature, 71.00 g n-BuLi solution (2M in cyclohexane, 0.183 mol) was charged through the dip leg below the surface of the gently agitated (300 rpm) toluene reaction mixture. The feed line was then flushed with 75 ml of anhydrous toluene. Next, 33.2 g of N,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.286 mol) was charged to the reactor through the subsurface feed line forming the characteristic bright red color of TMEDA complexed benzyl lithium anion with concomitant off gassing of butane. The subsurface line was flushed with a second 75 ml aliquot of anhydrous toluene via metering pump. An additional 350 ml of anhydrous toluene was fed at a constant rate during the anionic chain transfer polymerization process. Reactor agitation was increased to 510 rpm and 2939 g of styrene (99+%, 28.22 mol) were fed over 180 minutes. The well-calibrated metering pump was programmed to feed at a constant rate of 16.3 g/min. Anhydrous cyclohexane (2×200 ml) was charged to the styrene feed system to flush the alumina bed. The styrene feed to the reactor was deemed complete when no further heat of reaction was observed generally signified by the closing of the automated control valve on the cooling coils.
The set point of PID temperature controller was maintained at 80° C. and water was fed through the cooling coils as needed while the flow of the hot oil was altered to bypass the reactor jacket. The reaction mixture was quenched at 80° C. with a 50 ml aliquot of deoxygenated water resulting in a water white turbid mixture. The reaction mixture was washed with deoxygenated water (3×650 ml). Phase cuts were rapid and required little settling time. Water and any rag or emulsion was removed through the bottom drain valve.
The temperature of the oil jacket was increased to 130° C. while the control valve to the cooling coils was turned off. Cyclohexane, residual moisture and toluene were distilled through a simple distillation head (1 atm.) until a pot temperature of 115° C. was observed. An aliquot was removed for analysis via GPC (Mr: 306, Mn: 505, Mw: 824, Mz: 1314, PD: 1.63)
The crude reaction mixture, 7589 g, was stripped via continuous operation of excess toluene to yield 3382 g of an intermediate product stream that had the following GPC analysis: Mr: 305, Mn: 539, Mw: 852, Mz: 1342, PD: 1.58. The continuous strip was accomplished by means of wiped film evaporator (WFE, aka. Pope Still). WFE operating conditions were as follows: feed rate=1.33 L/hr, oil jacket temperature=185° C., Pressure=55 mm Hg and condenser temperature=0° C. An additional 1430 g of toluene was collected in a dry ice trap, while the cold finger condensed 2634 g of a mixture of toluene and 1,3-diphenylpropane.
A second pass of the concentrate through the WFE produced 3012 g of an oligomeric mixture with the following GPC profile: Mr: 409, Mn: 648, Mw: 928, Mz: 1390, PD: 1.43. WFE operating conditions were as follows: feed rate=1.33 L/hr, oil jacket temperature=205° C., Pressure=0.6 mm Hg and condenser temperature=0° C. A mixture (455 g) of 1,3-Diphenylpropane and its structural isomers (methylated diphenylethanes) were collected as a distillate.
Example 10
ACTSP-10 Mw=1194 PD=1.77
Toluene, 5798 g (6.7 liters, 62.92 mol) was charged to the reactor previously heated to 110° C. by means of the hot oil jacket. The PID controller operating the coiling coils was set for 115° C. As the solvent was heated to the reaction temperature, 79.6 g n-BuLi solution (2M in cyclohexane, 0.205 mol) was charged through the dip leg below the surface of the gently agitated (300 rpm) toluene reaction mixture. The feed line was then flushed with 75 ml of anhydrous toluene. Once the pot temperature reached 110° C., 24.2 g of N,N,N′,N′-tetramethylethylenediamine (TMEDA, 0.208 mol) was charged to the reactor through the subsurface feed line forming the characteristic bright red color of TMEDA complexed benzyl lithium anion with concomitant off gassing of butane. The subsurface line was flushed with a second 75 ml aliquot of anhydrous toluene via metering pump. Additionally 350 ml of anhydrous toluene was fed at a constant rate during the anionic chain transfer polymerization process. Reactor agitation was increased to 510 rpm and 2544 g of styrene (99+%, 24.43 mol) were fed over 80 minutes. The well-calibrated metering pump was programmed to feed at a constant rate of 31.8 g/min. Anhydrous cyclohexane (2×200 ml) was charged to the styrene feed system to flush the alumina bed. The styrene feed to the reactor was deemed complete when no further heat of reaction was observed generally signified by the closing of the automated control valve on the coiling coils.
The PID temperature controller was set at 80° C. and water was fed through the cooling coils while the flow of the hot oil was altered to bypass the reactor jacket. The reaction mixture was quenched at 80° C. with a 50 ml aliquot of deoxygenated water resulting in a water white turbid mixture. The reaction mixture was washed with deoxygenated water (3 times, 650 ml). Phase cuts were rapid and required little settling time. Water and any rag or emulsion was removed through the bottom drain valve.
The temperature oil jacket was increased to 130° C. while the control valve to the cooling coils turned off. Cyclohexane, residual moisture and toluene were distilled through a simple distillation head (1 atm.) until a pot temperature of 115° C. was observed. An aliquot was removed for analysis via GPC (Mr: 397, Mn: 652, Mw: 1174, Mz: 1853, PD: 1.80)
The crude reaction mixture, 8967 g, was stripped via continuous operation of excess toluene to yield 2846 g of the concentrated product stream that had the following GPC analysis: Mr: 295, Mn: 674, Mw: 1194, Mz: 1877, PD: 1.77. The continuous strip was accomplished by means of wiped film evaporator (WFE, aka. Pope Still). WFE operating conditions were as follows: feed rate=1.33 L/hr, oil jacket temperature=160° C., Pressure=90 mm Hg and condenser temperature=0° C. Additionally 1024 g of toluene was collected in a dry ice trap, while the cold finger condensed 5002 g of a mixture of toluene and 1,3-diphenylpropane.
Examples 11 and 12 Continuous Mode
Example 11
ACTSP-11 Mw=4054 PD=2.14
The apparatus was a glass 200 mL oil jacketed baffled cylindrical reactor with an overflow port equipped with a nitrogen inlet, overhead stainless steel stirring shaft with pitched blade turbine impeller, and a thermal couple. The reactor was also outfitted with two subsurface feed lines: (1) a stainless steel 1⁄8′′ (32 mm) O.D. line for introducing a mixture of styrene and toluene; and (2) a stainless steel 1/16′′ (16 mm) O.D. line for feeding a mixture formed from butyl lithium TMEDA and toluene. The 1/16′′ (16 mm) line was threaded through a 1⁄4′′ (6.4 mm) line to prevent entanglement with the mechanical stirring apparatus during the course of a run. The tip of the 1/16 inch (16 mm) feed line was directed just below the impeller. The overflow port was directed downward at a 22.5° angle, and was attached by means of a 13 mm Ace Thread® Teflon® connection to a 24-inch long glycol jacketed 15 mm O.D. glass tube. The other end of the 15 mm glass tube was connected to a 2 liter, glycol jacketed stirred reactor by means of a second 13 mm Ace Thread® Teflon® connection (neither Teflon® couplings were wetted parts). The overflow reactor was equipped with an all-glass overhead stirring apparatus, bottom drain valve, chilled water condenser, and nitrogen oil-bubbler outlet. The overflow line and reactor were heated to 100° C. with glycol.
In a stirred, oven-dried pear-shaped 500 ml flask under an inert N2 atmosphere at ambient temperature, an organolithium mixture was formed from 91.75 g (106 mL, 1.09 mol) of anhydrous toluene, 42.98 mL of 16.5 wt % (5.28 g, 0.0824 mol contained alkyl lithium) n-butyl lithium in cyclohexane and 8.62 g (11.19 mL, 0.0742 mole) TMEDA; this mixture was stirred with a glass coated (no PTFE) magnetic stirring bar. About one half of the solution was drawn through a 1/16′′ (16 mm) stainless steel three-way ball valve into an oven dried 100 ml glass syringe mounted on a syringe pump. After infusion of the syringe, the ball valve was lined up such that the path from the syringe to the 1/16′′ (16 mm) subsurface feed line in the reactor was open and the path to the magnetically stirred flask was closed. During the course of a reaction, the infusion of the syringe with the second half of the mixture was achieved by lining the 3-way ball valve such that the path to the flask was open and the path to the reactor was closed.
At the start of the run, the reactor was charged with 100 mL of anhydrous toluene and heated to 110° C. Meanwhile, 547 g (602 mL, 5.25 mol) of styrene and 1734 g (2000 mL, 20.6 mol) of anhydrous toluene were combined, mixed and then charged to a N2-blanketed 3000 ml graduated cylinder reservoir. The toluene-styrene mixture was pumped to the reactor with a laboratory-metering pump through a column of anhydrous basic alumina until the first drop or two were seen entering the reactor; the feed was stopped and stirring in the reactor was initiated ( ̃400 rpm). Butyl lithium in cyclohexane was charged dropwise into the reactor by means of a 1.0 mL syringe. The addition was stopped when the characteristic red color of the polystyryllithium anion appeared (indicating anhydrous conditions). Next, about 4.8 g (0.012 mol) of 16.5 wt % n-butyl lithium and 1.3 g (0.011 mol) of TMEDA were charged to the reactor. The feed rates of both feeds (toluene-styrene mixture and organolithium mixture) were preset (toluene-styrene mixture: 6.28 mL/min; organolithium mixture: 0.386 mL/min) and the pumps were calibrated such that 200 ml of combined feed passed through the reactor per hour (two reactor volumes per hour) for a 30-minute residence time. The process was conducted for about 195 minutes at 110° C.
Samples were collected approximately every 30 minutes after the first 45-minute period. It was found that within two reactor volumes, the system had reached steady state conditions. The GPC molecular weight distribution of the first fraction collected was as follows: Mw=1992, Mp=2209, Mn=716 Daltons, Mz=3512 and Polydispersity=2.78. A typical steady state fraction analyzed as follows: Mw=4146, Mp=4507, Mn=1656, Mz=7134 Daltons and Polydispersity=2.50. GPC analysis of a composite of steady state fractions analyzed after stripping toluene and 1-3-diphenylpropane was as follows: Mw=4051, Mp=3822, Mn=1879, Mz=6897 Daltons and Polydispersity=2.15
Example 12
ACTSP-12 Mw=2288 PD=1.91
The run in this Example repeats that of Example 11, except as described herein. The toluene-styrene mixture was made from 547 g (602 mL, 5.25 mol) of styrene and 1816 g (2100 mL, 21.58 mol) of anhydrous toluene. The organolithium mixture was formed from 177.27 g (2.11 mol, 205 mL) of anhydrous toluene, 90.26 mL of 16.5 wt % (11.08 g, 0.173 mol contained alkyl lithium) n-butyl lithium in cyclohexane and 24.81 g (19.10 mL, 0.1644 mole) TMEDA. After the red color of the polystyryllithium anion appeared, about 10 g (0.024 mol) of 16.5 wt % n-butyl lithium and 2.6 g (0.022 mol) of TMEDA were charged to the reactor. The feed rates of both feeds were preset (toluene-styrene mixture: 6.28 mL/min; organolithium mixture: 0.764 mL/min). The combined feed rate was one reactor volume (200 ml) per 28.4 minutes. The process was conducted for about 419 minutes at 110° C.-113° C.
Samples were collected approximately every 30 minutes after the first 45 minute period. It was found that within two reactor volumes, the system had reached steady state conditions. The GPC molecular weight distribution of the first fraction collected was as follows: Mw=2154, Mp=2293, Mn=953, Mz=3510 Daltons and Polydispersity=1.65. A typical steady state fraction analyzed as follows: Mw=2395, Mp=2410, Mn=1026, Mz=4246 Daltons and Polydispersity=2.34. GPC analysis of a composite of steady state fractions analyzed after stripping toluene and 1-3-diphenylpropane was as follows: Mw=2288, Mp=2094, Mn=1200, Mz=3767 Daltons and Polydispersity=1.91.
BROMINATION
General Description:
Bromochloromethane (BCM) was azeotropically dried (5-10 ppm moisture by Karl Fisher). All feed lines, feed tanks and glassware were dried (oven dried at 130° C. min 2 hour where appropriate) and purged over-night prior to use in the bromination reaction. All glassware, feed lines, and feed tanks are maintained under a N2 atmosphere during the course of the set-up and the operation of the bromination reactor.
The amount of AlBr3 catalyst (commercially available) needed to make a 0.25 mole % (calculated using the formula [moles AlBr3/moles Br2]*100%=0.25% mole % AlBr3) solution of active catalyst was weighed and then transferred to oven dried reagent bottles in a nitrogen-purged glove box. By active catalyst, it is meant that amount of catalyst above any additional amount that would be otherwise deactivated by moisture either in the bromine itself or any other process stream involved in the bromination reaction. Bromine (5-10 ppm moisture content) was pumped into the reagent bottle containing the AlBr3 and then stirred with a PTFE coated magnetic stirring bar for 30 minutes to assure homogenous dissolution of the catalyst. The 0.25 mole % AlBr3 in bromine solution was then transferred to a graduated feeding vessel placed on a large capacity laboratory balance.
The anionic chain-transfer styrene polymer (ACTSP) used was dissolved in dry (5-10 ppm moisture) BCM to make a 25-wt % solution. The solution was then charged to a graduated feeding vessel. The 0.25 mole % AlBr3 in bromine and the 25 wt % ACTSP in BCM solution are co-fed via separate peristaltic pumps through 1⁄8′′ (32 mm) O.D. feed lines to a well-stirred fresh or recycle heel of anhydrous BCM at 0° C.-10° C. The relative feed rates are constantly monitored such that ratio of the two reagents fed remains constant or near constant during the course of the electrophilic bromination reaction.
Bromination Equipment Set-up:
A 5 L oil jacketed flask (bromination reactor) was equipped with an over head glass stirrer shaft, PTFE stirring paddle, a water-cooled condenser, thermo-well, nitrogen inlet, and bottom drain valve. The reactor was vented through a calcium sulfate moisture trap to a well-stirred caustic scrubber to absorb co-product HBr and entrained Br2. Additionally the reactor was outfitted with three inlet lines: 1) 1⁄4′′ (6.4) O.D. PTFE BCM feed for initial feed of BCM to the reactor (the BCM can be either fresh or a BCM recycle heel from a previous run); 2) 1⁄8′′ (32 mm) O.D. substrate/BCM subsurface feed line; and 3) 1⁄8′′ (32 mm) O.D. Br2/AlBr3 subsurface feed line. The AlBr3/Br2 and ACTSP/BCM feed lines are secured such that both inlet lines discharge their contents in close proximity creating a locally high reagent concentration. The bromination reactor was completely covered with aluminum foil to exclude light and the reaction was conducted in a darkened ventilation hood.
The bromination reactor was placed above a 6-liter water quench pot with a 3⁄8′′ (9.5 mm) O.D. PTFE drain line that connects the bottom drain valve of the bromination reactor to the quench pot to allow for direct transfer of the bromination reactor's contents. The quench pot was oil jacketed and equipped with an over-head stirring mechanism, thermowell, sodium bisulfite addition funnel and was baffled for intimate mixing of organic and aqueous phases. The quench pot had a nitrogen inlet and was purged to a caustic scrubber. The quench pot had a bottom drain valve to enable transfer of the pot's contents to an intermediate 5 liter storage vessel.
The intermediate storage vessel was piped to transfer its contents to a wash kettle. The wash kettle was a 6-liter oil-jacketed, baffled reactor outfitted with an over-head stirrer, reverse phase Dean Stark trap, thermocouple and bottom drain valve.
Alternative pieces of equipment are suitable for recovering the brominated product as a solid and essentially free of BCM. Product recovery can be effected by distilling off the BCM in an oil jacketed resin kettle to form a concentrate. The kettle is located to enable its concentrate product to in turn be dropped as a melt into a bucket of well-stirred (high shear) cold water. The stirring produces a granular (chopped) product (after oven drying) that is suitable for compounding into a formulation. The alternative set-up provides a water-containing vessel into which unconcentrated product is fed accompanied by the concomitant azeotropic removal of BCM. The granules from the first and the precipitate from the second, are passed through a vacuum oven for drying Materials with glass transition temperature (Tg) below 100° C. are rinsed with methanol before drying in the oven at a temperature 15° C. below their Tg.
A recapitulation of process parameters and analytical data on the final compositions contained for each of the Bromination Examples is found in Table I.
Bromination Example 1
To the 5 L bromination reactor described above was charged 867 g of dry BCM (azeotropically dried to 5-10 ppm moisture, Karl Fisher). The BCM was cooled in the dark to −1° C. and a previously prepared 25 wt % solution comprised of 334 g of ACTSP-1 (From ACTSP Example 1 Mw=483, PD=1.32) and 1002 g of dry BCM was charged to a dry, 2000 ml N2 blanketed graduated cylinder outfitted with a 1⁄8′′ (32 mm) PTFE feed line placed to transfer the entire content of the cylinder by means of a peristaltic metering pump to the bromination reactor. The previously prepared AlBr3 (0.25 mol %) in bromine (1356 g) was transferred via a peristaltic pump into a 1.5 liter graduated cylinder. This feed vessel was maintained under a N2 atmosphere and was outfitted with a 1⁄8′′ (32 mm) PTFE feed line placed to transfer the desired amount of bromine solution by means of a peristaltic metering pump to the bromination reactor.
The two reagents are co-fed at predetermine relative rates such that the entire content of the two feeds are charged and simultaneously completed in 180 minutes. The co-feed was interrupted and the entire content of the reactor transferred to the quench pot on 60-minute intervals resulting in a 30-minute average residence time for the reagents. A new heel was created in the bromination flask of 867 g of dry BCM each time prior to resumption of the cofeed. Ample cooling was provided through out the operation such that the reaction temperature remains close to −3° C. Upon completion of the feed the reaction was allowed to stir for an additional 5 minutes to allow unreacted bromine to be consumed. The reaction mixture was transferred (gravity) to the 6 L quench pot through the bottom drain valve and the 3⁄8′′ (9.5 mm) O.D. PTFE transfer line.
The quench pot was previously charged with 1000 ml tap water (25° C.) and stirred at 400 rpm to assure intimate mixing of the organic and aqueous phase. Upon completion of the transfer, 10% Na2SO3 solution was added until the red color was eliminated and a near water white mixture was observed. The quench was exothermic and a 10° C. temperature rise was observed. Agitation was stopped and the organic phase allowed to settle. The lower organic phase was transferred to a 5 L storage vessel containing 1000 ml of 10% NaOH and 1.0 g NaBH4.
This two-phase system was then transferred to the 6 L wash kettle and refluxed (62° C.) for 30 minutes. Agitation was interrupted and the bottom organic layer cut from the reactor. The organic layer was returned to the completely drained kettle and washed twice with 1000 ml of tap water to a pH of 10. The solution was then azeotropically dried by means of a reverse phase Dean-Stark trap. The content of the reactor was pumped to a 1 liter resin kettle while stripping BCM at atmospheric pressure. Upon completion of the transfer, the BCM strip was continued at atmospheric pressure until the pot temperature reached 150° C. BCM was then further removed in vacuo to an ending condition of 150° C. and <5 mm Hg.
The content of the resin kettle was drained into a 2.5-gallon plastic pail of rapidly stirred (high sheer blade, 2100 rpm) cold water to grind the product into a coarse powder. The product was collected in a 3000 ml coarse fitted Büchner funnel, rinsed with methanol and then dried in a vacuum oven (25° C.) to yield 955 g of the brominated product.
Bromination Example 2
The procedure of Bromination Example 1 was used except that 2000 g of a 25 wt % solution of ACTSP-1 (From ACTSP Example 1 Mw=483, PD=1.32) in dry BCM was co-fed with 257 g of 0.25 mole % AlBr3 in bromine to a heel of 3850 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was dried at 45° C. in a vacuum oven. The procedure produced 1688 g of product.
Bromination Example 3
The procedure of Bromination Example 1 was used except that 2000 g of a 25 wt % solution of ACTSP-1 (From ACTSP Example 1 Mw=483, PD=1.32) in dry BCM was co-fed with 2846 g of 0.25 mole % AlBr3 in bromine to a heel of 3850 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was dried at 65° C. in a vacuum oven. The procedure produced 1823 g of product.
Bromination Example 4
The procedure of Bromination Example 1 was used except that 1500 g of a 25 wt % solution of ACTSP-2 (From ACTSP Example 2 Mw=496, PD=1.32) in dry BCM was co-fed with 2895 g of 0.25 mole % AlBr3 in bromine to a heel of 3500 g of BCM at a constant uninterrupted relative feed rate so that the average residence time in the reactor was 90 minutes. The crude product mixture was heterogeneous and required the addition of 0.125 g of sodium dodecyl sulfate to each aqueous wash to break the resulting emulsions and achieve the desired phase cut. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 130° C. in a vacuum oven. The procedure produced 1645 g of product.
Bromination Example 5
The procedure of Bromination Example 1 was used except that 1165 g of a 25 wt % solution of ACTSP-2 (From ACTSP Example 2 Mw=496, PD=1.32) in dry BCM was co-fed with 2330 g of 0.25 mole % AlBr3 in bromine to a heel of 3200 g of BCM at a constant uninterrupted relative feed rate so that the average residence time in the reactor during the feed was 90 minutes. The reaction mixture was allowed to stir for an additional 60 minutes after completion of the co-feed. The crude product mixture was heterogeneous and required the addition of 0.125 grams of sodium dodecyl sulfate to each aqueous wash to break the resulting emulsions and achieve the desired phase cut. The washed product mixture was filtered and the resulting filter cake washed with BCM and dried in a vacuum oven at 150° C. to yield 557 g of a white solid. The filtrate and wash BCM were combined and the soluble portion of the product precipitated from water at 95° C. with concomitant stripping of BCM. The BCM-soluble product fraction was dried at 130° C. in a vacuum oven to yield 693 g of a white solid.
Bromination Example 6
The procedure of Bromination Example 1 was used except that 2000 g of a 25 wt % solution of ACTSP-3 (From ACTSP Example 3 Mw=530, PD=1.47) in dry BCM was co-fed with 2846 g of 0.25 mole % AlBr3 in bromine to a heel of 4000 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was dried at 65° C. in a vacuum oven. The procedure produced 1730 g of product.
Bromination Example 7
The procedure of Bromination Example 1 was used except that 2000 g of a 25 wt % solution of ACTSP-3 (From ACTSP Example 3 Mw=530, PD=1.47) in dry BCM was co-fed with 2704 g of 0.25 mole % AlBr3 in bromine to a heel of 4000 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was dried at 45° C. in a vacuum oven. The procedure produced 1751 g of product.
Bromination Example 8
The procedure of Bromination Example 1 was used except that 2000 g of a 25 wt % solution of ACTSP-3 (From ACTSP Example 3 Mw=530, PD=1.47) in dry BCM was co-fed with 2846 g of 0.25 mole % AlBr3 in bromine to a heel of 4200 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was dried at 45° C. in a vacuum oven. The procedure produced 1853 g of product.
Bromination Example 9
The procedure of Bromination Example 1 was used except that 1336 g of a 25 wt % solution of ACTSP-4 (From ACTSP Example 4 Mw=584, PD=1.50) in dry BCM was co-fed with 1356 g of 0.25 mole % AlBr3 in bromine to a heel of 2600 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was dried at 30° C. in a vacuum oven. The procedure produced 933 g of product.
Bromination Example 10
The procedure of Bromination Example 1 was used except that 2000 g of a 25 wt % solution of ACTSP-4 (From ACTSP Example 4 Mw=584, PD=1.50) in dry BCM was co-fed with 2333 g of 0.25 mole % AlBr3 in bromine to a heel of 4000 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was dried at 35° C. in a vacuum oven. The procedure produced 1540 g of product.
Bromination Example 11
The procedure of Bromination Example 1 was used except that 2000 g of a 25 wt % solution of ACTSP-4 (From ACTSP Example 4 Mw=584, PD=1.50) in dry BCM was co-fed with 2846 g of 0.25 mole % AlBr3 in bromine to a heel of 4200 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was dried at 60° C. in a vacuum oven. The procedure produced 1677 g of product.
Bromination Example 12
The procedure of Bromination Example 1 was used except that 2000 g of a 25 wt % solution of ACTSP-4 (From ACTSP Example 4 Mw=584, PD=1.50) in dry BCM was co-fed with 3167 g of 0.25 mole % AlBr3 in bromine to a heel of 3850 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was dried at 65° C. in a vacuum oven. The procedure produced 1640 g of product.
Bromination Example 13
The procedure of Bromination Example 1 was used except that 2000 g of a 25 wt % solution of ACTSP-5 (From ACTSP Example 5 Mw=715, PD=1.40) in dry BCM was co-fed with 2125 g of 0.25 mole % AlBr3 in bromine to a heel of 3800 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was dried at 60° C. in a vacuum oven. The procedure produced 1462 g of product.
Bromination Example 14
The procedure of Bromination Example 1 was used except that 2000 g of a 25 wt % solution of ACTSP-5 (From ACTSP Example 5 Mw=715, PD=1.40) in dry BCM was co-fed with 2571 g of 0.25 mole % AlBr3 in bromine to a heel of 4000 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was dried at 70° C. in a vacuum oven. The procedure produced 1601 g of product.
Bromination Example 15
The procedure of Bromination Example 1 was used except that 1600 g of a 25 wt % solution of ACTSP-5 (From ACTSP Example 5 Mw=715, PD=1.40) in dry BCM was co-fed with 2276 g of 0.25 mole % AlBr3 in bromine to a heel of 3500 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 90° C. in a vacuum oven. The procedure produced 1427 g of product.
Bromination Example 16
The procedure of Bromination Example 1 was used except that 2000 g of a 25 wt % solution of ACTSP-6 (From ACTSP Example 6 Mw=740, PD=1.66) in dry BCM was co-fed with 2846 g of 0.25 mole % AlBr3 in bromine to a heel of 4200 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was precipitated from water at 92° C. with concomitant stripping of BCM. The product was dried at 90° C. in a vacuum oven. The procedure produced 1820 g of product.
Bromination Example 17
The procedure of Bromination Example 1 was used except that 1500 g of a 25 wt % solution of ACTSP-7 (From ACTSP Example 7 Mw=800, PD=1.39) in dry BCM was co-fed with 1836 g of 0.25 mole % AlBr3 in bromine to a heel of 3000 g of BCM at a constant and uninterrupted relative feed rate so that the average residence time in the reactor was 90 minutes. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 90° C. in a vacuum oven. The procedure produced 1250 g of product.
Bromination Example 18
The procedure of Bromination Example 1 was used except that 1500 g of a 25 wt % solution of ACTSP-7 (From ACTSP Example 7 Mw=800, PD=1.39) in dry BCM was co-fed with 2135 g of 0.25 mole % AlBr3 in bromine to a heel of 3000 g of BCM at a constant and uninterrupted relative feed rate so that the average residence time in the reactor was 90 minutes. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 110° C. in a vacuum oven. The procedure produced 1400 g of product.
Bromination Example 19
The procedure of Bromination Example 1 was used except that 1500 g of a 25 wt % solution of ACTSP-7 (From ACTSP Example 7 Mw=800, PD=1.39) in dry BCM was co-fed with 2135 g of 0.25 mole % AlBr3 in bromine to a heel of 3000 g of BCM at a constant and uninterrupted relative feed rate so that the co-feed was completed in 180 minutes. Upon completion of the feed the reaction mixture was warmed to 25° C. over a 1 hr period, thus providing an average residence time in excess of 120 minutes. The product mixture was transferred to the quench pot and no sulfite was added to treat unreacted bromine. Unreacted bromine was converted to bromide during the caustic NaBH4 wash. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 110° C. in a vacuum oven. The procedure produced 1401 g of product.
Bromination Example 20
The procedure of Bromination Example 1 was used except that 1500 g of a 25 wt % solution of ACTSP-7 (From ACTSP Example 7 Mw=800, PD=1.39) in dry BCM was co-fed with 2375 g of 0.25 mole % AlBr3 in bromine to a heel of 3000 g of BCM at a constant and uninterrupted relative feed rate so that the co-feed was completed in 180 minutes. Upon completion of the feed the reaction mixture was warmed to 25° C. over a 1 hr period, thus providing an average residence time in excess of 120 minutes. The crude product mixture was heterogeneous and required the addition of 0.125 grams of sodium dodecyl sulfate to each aqueous wash to break the resulting emulsions and achieve the desired phase cut. The product mixture was transferred to the quench pot and no sulfite was added to treat unreacted bromine. Unreacted bromine was converted to bromide during the caustic NaBH4 wash. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 110° C. in a vacuum oven. The procedure produced 1460 g of product.
Bromination Example 21
The procedure of Bromination Example 1 was used except that 1500 g of a 25 wt % solution of ACTSP-8 (From ACTSP Example 8 Mw=817, PD=1.26) in dry BCM was co-fed with 1836 g of 0.25 mole % AlBr3 in bromine to a heel of 3000 g of BCM at a constant and uninterrupted relative feed rate so that the average residence time in the reactor was 90 minutes. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 100° C. in a vacuum oven. The procedure produced 1230 g of product.
Bromination Example 22
The procedure of Bromination Example 1 was used except that 1500 g of a 25 wt % solution of ACTSP-8 (From ACTSP Example 8 Mw=817, PD=1.26) in dry BCM was co-fed with 2135 g of 0.25 mole % AlBr3 in bromine to a heel of 3000 g of BCM at a constant and uninterrupted relative feed rate so that the average residence time in the reactor was 90 minutes. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 110° C. in a vacuum oven. The procedure produced 1320 g of product.
Bromination Example 23
The procedure of Bromination Example 1 was used except that 1500 g of a 25 wt % solution of ACTSP-8 (From ACTSP Example 8 Mw=817, PD=1.26) in dry BCM was co-fed with 2659 g of 0.25 mole % AlBr3 in bromine to a heel of 3000 g of BCM at a constant and uninterrupted relative feed rate so that the average residence time in the reactor was 90 minutes. The crude product mixture was heterogeneous and required the addition of 0.125 grams of sodium dodecylsulfate to each aqueous wash to break the resulting emulsions and achieve the desired phase cut. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 130° C. in a vacuum oven. The procedure produced 1440 g of product.
Bromination Example 24
The procedure of Bromination Example 1 was used except that 1500 g of a 25 wt % solution of ACTSP-9 (From ACTSP Example 9 Mw=928, PD=1.43) in dry BCM was co-fed with 1836 g of 0.25 mole % AlBr3 in bromine to a heel of 3000 g of BCM at a constant and uninterrupted relative feed rate so that the average residence time in the reactor was 90 minutes. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 100° C. in a vacuum oven. The procedure produced 1250 g of product.
Bromination Example 25
The procedure of Bromination Example 1 was used except that 1500 g of a 25 wt % solution of ACTSP-9 (From ACTSP Example 9 Mw=928, PD=1.43) in dry BCM was co-fed with 2135 g of 0.25 mole % AlBr3 in bromine to a heel of 3000 g of BCM at a constant and uninterrupted relative feed rate so that the average residence time in the reactor was 90 minutes. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 110° C. in a vacuum oven. The procedure produced 1388 g of product.
Bromination Example 26
The procedure of Bromination Example 1 was used except that 1500 g of a 25 wt % solution of ACTSP-9 (From ACTSP Example 9 Mw=928, PD=1.43) in dry BCM was co-fed with 2659 g of 0.25 mole % AlBr3 in bromine to a heel of 3000 g of BCM at a constant and uninterrupted relative feed rate so that the average residence time in the reactor was 90 minutes. The crude product mixture was heterogeneous and required the addition of 0.125 grams of sodium dodecylsulfate to each aqueous wash to break the resulting emulsions and achieve the desired phase cut. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 130° C. in a vacuum oven. The procedure produced 150 g of product.
Bromination Example 27
The procedure of Bromination Example 1 was used except that 1400 g of a 25 wt % solution of ACTSP-10 (From ACTSP Example 9 Mw=1194, PD=1.77) in dry BCM was co-fed with 1800 g of 0.25 mole % AlBr3 in bromine to a heel of 3200 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 105° C. in a vacuum oven. The procedure produced 89 g of product.
Bromination Example 28
The procedure of Bromination Example 1 was used except that 1400 g of a 25 wt % solution of ACTSP-10 (From ACTSP Example 9 Mw=1194, PD=1.77) in dry BCM was co-fed with 2045 g of 0.25 mole % AlBr3 in bromine to a heel of 4000 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 120° C. in a vacuum oven. The procedure produced 1245 g of product.
Bromination Example 29
The procedure of Bromination Example 1 was used except that 1392 g of a 25 wt % solution of ACTSP-11 (From ACTSP Example 11 Mw=4051, PD=2.15) in dry BCM was co-fed with 1479 g of 0.25 mole % AlBr3 in bromine to a heel of 3000 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 130° C. in a vacuum oven. The procedure produced 980 g of product.
Bromination Example 30
The procedure of Bromination Example 1 was used except that 1360 g of a 25 wt % solution of ACTSP-12 (From ACTSP Example 12 Mw=2288, PD=1.91) in dry BCM was co-fed with 1445 g of 0.25 mole % AlBr3 in bromine to a heel of 3200 g of BCM at a constant relative feed rate so that the average residence time in the reactor was 30 minutes. The product was precipitated from water at 95° C. with concomitant stripping of BCM. The product was dried at 115° C. in a vacuum oven. The procedure produced 1002 g of product.









TABLE I









Bromination example


















1
2
3
4
5
6
7
8
9
10





ACTSP Example
1
1
1
2
2
3
3
3
4
4


ACTSP Mw
483
483
483
496
496
530
530
530
584
584


ACTSP PD
1.32
1.32
1.32
1.32
1.32
1.47
1.47
1.47
1.50
1.50


ACTSP (g)
334
500
500
375
291.3
500
500
500
334
500


Moisture (ppm)
58
66
66
5
5
26
26
26
14
11 ppm


Wt % in BCM
25
25
25
25
25
25
25
25
25
25


BCM in Feed (g)
1002
1500
1500
1125
873.9
1500
1500
1500
1002
1500


Bromine (g)
1356.24
2571.43
2846.15
2895.3
2330.4
2846.15
2703.7
2846.15
1356.24
2333.3


BCM in Reactor
2600
3850
4200
3500
3200
4000
4000
4200
2600
4000


(g)


Rxn Temp
−3 
−2 
−2 
−5 
−3 (−6~−1.1)
−5 
−4 
−4 (−6~−2)
−3 (−4~−2)
−4 (−6~−1)


(range ° C.)
(−4~−2)
(−4~−1)
(−4~−1)
(−6~−2)

(−6~−3.5)
(−5.3~−3)


Average
30
30
30
90
>120
30
30
30
30
30


residence


time(min)


















Solids from ML
103
0
0
0
557
0
50.3
0
0
0
180.5


(g)







part
part







a
b


Mass of Product
954.9
1688.11
1823.53
1550
557
693
1730.2
1751.9
1853.2
933.05
1540.75


Theoretical Yield
1012
1806
1923
1645
(a + b)
1306
1819
1880
1976
1044
1678

















% Yield
105%
93%
95%
94%
96%
98%
93%
94%
89%
103%












Bromination example


















Product Analyses
1
2
3
4
5a
5b
6
7
8
9
10





Residual BCM (ppm)
270
430
220
960
2830
90
240

17600
3750
310


XRF wt % Br
68.3
73.2
74.3
78.4
N/A
78.7
75.1
72.5
74.7
68.5
71.1


bromine per ring
2.7
3.5
3.7
4.6

4.7
3.8
3.4
3.7
2.8
3.1


Tg (° C.) (DSC)
37.7
57.4
74.66
139
222
140.86
72.3
60.76
52.44
38.06
43.23


TGA (N2)


 1% Wt. Loss (° C.)
230
259
273
322
320
331
268
258
154
169
212


 5% Wt. Loss (° C.)
290
308
327
365
362
367
318
311
300
283
292


10% Wt. Loss
317
334
354
380
375
380
342
337
335
314
323


(° C.)


50% Wt. Loss
390
391
395
418
415
412
395
398
394
398
384


(° C.)


Thermal HBr
73
349
248
314
208
363
463
333
315
131
<50


300° C. (ppm)


GPC


Mw
1552
2092
2180
3041
N/A
3066
1561
2359
2410
2014
2250


Mn
958
1819
1880
2605
N/A
2596
1391
2013
1700
1560
2040


Mz
2060
2549
2787
3713
N/A
3792
1922
2945
4250
2677
2585


PD
1.6
1.15
1.16
1.17
N/A
1.18
1.12
1.17
1.4
1.29
1.1


Color (YI Powder)

2.82
3.66






6.88


Color (solution)


L
100.36
98.98
98.55
98.69
N/A
97.4
99.08
97.32
96.98
96.79
96.2


a
0.01
−0.06
−0.1
−0.65
N/A
−1.52
−0.47
−0.19
−0.32
−0.96
−0.9


b
0.74
2.47
3.33
4.9
N/A
9.97
6.5
6.07
7.79
5.7
8.08


ΔE
0.82
2.67
3.63
5.11
N/A
10.41
6.58
6.64
8.36
6.61
8.97












Bromination example


















11
12
13
14
15
16
17
18
19
20





ACTSP Example
4
4
5
5
5
6
7
7
7
7


ACTSP Mw
584
584
715
715
715
740
800
800
800
800


ACTSP PD
1.50
1.50
1.40
1.40
1.40
1.66
1.39
1.39
1.39
1.39


ACTSP (g)
500
500
500
500
400
500
375
375
375
375


Moisture (ppm)
11
11
9
9
9
11
19
19
19
19


Wt % in BCM
25
25
25
25
25
25
25
25
25
25


BCM in Feed (g)
1500
1500
1500
1500
1200
1500
1125
1125
1125
1125


Bromine (g)
2846.15
3166.67
2125
2571.43
2276
2846.15
1836.2
2134.6
2134.6
2375


BCM in Reactor
4200
3850
3800
4000
3500
4200
3000
3000
3000
3000


(g)


Rxn Temp
−4 
−2 
−5.5 (−7~−3)
−5 
−3 (−4~−1)
−4 (−6~−2)
−4 (−5~−2)
−4 (−5~−2)
−4 (−5~−2)
−4 (−5~−2)


(range ° C.)
(−6~−1)
(−4~−1)

(−6~−3)


Average
30
30
30
30
30
30
90
90
>120
>120


residence


time(min)


Solids from ML
33.37
113.04
0
0
0
0
0
0
0


(g)


Mass of Product
1677.7
1641.0
1462.9
1601.5
1426.8
1820.0
1250.0
1400.1
1401.0
1460


Theoretical Yield
1880
1986
1582
1736
1556
2000
1307
1448
1465
1563


% Yield
91%
88%
92%
92%
92%
91%
96%
97%
96%
93%


Product Analyses


Residual BCM
270
190
250
220
7520
1200
29
0
84
<30


(ppm)


XRF wt % Br
74.1
75.5
68.4
71.7
74.2
76.2
72.3
74.7
75.2
76.5


bromine per ring
3.6
3.9
2.8
3.2
3.7
4.1
3.3
3.8
3.9
4.2


Tg (° C.) (DSC)
73.11
93.11
75.33
87.94
111.1
102.02
104.6
131.7
136.9
158.1


TGA (N2)


 1% Wt. Loss
236
265
316
314
210
273
273
339
341
347


(° C.)


 5% Wt. Loss
306
334
351
348
351
339
320
366
370
375


(° C.)


10% Wt. Loss
335
357
363
361
365
360
339
378
380
386


(° C.)


50% Wt. Loss
388
401
393
393
401
406
382
411
410
416


(° C.)


Thermal HBr
357
199
251
<50
254
160
347
163
158
<50


300° C. (ppm)


GPC


Mw
2100
2990
2630
2840
3109
4000
3050
3280
3510
3599


Mn
1200
2440
2170
2180
2665
3160
2530
2720
2663
2780


Mz
3713
3963
3460
3918
3815
5460
3720
4020
4815
4871


PD
1.75
1.23
1.21
1.30
1.17
1.30
1.20
1.21
1.32
1.29


Color







3.98


(YI Powder)


Color (solution)


L
98.34
98.48
95.02
95.18
100.3
99.58
100.05
100.95
99.5
98.61


a
−1.95
−1.94
−1.79
−1.49
−2.59
−0.18
0.05
−0.11
−0.36
−0.76


b
8.77
11.48
14.58
15.67
7.56
1.45
0.46
0.51
2.18
4.76


ΔE
9.14
11.74
15.51
16.46
8.00
1.52
0.47
1.08
2.27
5.02












Bromination example


















21
22
23
24
25
26
27
28
29
30





ACTSP Example
8
8
8
9
9
9
10
10
11
12


ACTSP Mw
817
817
817
928
928
928
1194
1194
4054
2288


ACTSP PD
1.27
1.27
1.27
1.43
1.43
1.43
1.77
1.77
2.15
1.91


ACTSP (g)
375
375
375
375
375
375
350
350
348
340


Moisture (ppm)
89
89
89
12
12
12
12
12
145
94


Wt % in BCM
25
25
25
25
25
25
25
25
25
25


BCM in Feed (g)
1125
1125
1125
1125
1125
1125
1050
1050
1044
1020


Bromine (g)
1836
2135
2659
1836
2135
2659
1800
2045
1479
1445


BCM in Reactor
3000
3000
3000
3000
3000
3500
3200
4000
3200
3000


(g)


Rxn Temp
−4 
−4 
−4 
−5 
−5 
−4.7 
−3.8 (−4~−2)
−3.8 (−4~−2)
−3.8 (−5~−3)
−3.8 (−4~−2)


(range ° C.)
(−6~−2.5)
(−6~−2.5)
(−6~−2.5)
(−6~−2)
(−6~−2)
(−6~2)


Average
90
90
90
90
90
90
30
30
30
30


residence


time(min)


Solids from ML
0
0
0
0
0
0
0
0
0
0


(g)


Mass of Product
1230
1320
1440
1250
1388
1500
891
1244.53
980.5
1002.25


Theoretical Yield
1339
1442
1563
1339
1500
1563
1296
1346
1094
1063


% Yield
92%
92%
92%
93%
93%
96%
69%
92%
90%
94%


Product Analyses


Residual BCM
<50
30
70
0
0
90
<50
160
1550
320


(ppm)


XRF wt % Br
72.5
74.4
76.4
72.7
73.5
77.5
73.1
74.6
68.6
68.6


bromine per ring
3.4
3.7
4.1
3.4
3.6
4.4
3.5
3.7
2.8
2.8


Tg (° C.) (DSC)
112.3
137.2
163.02
112.6
142.5
163.1
117.44
140.35
150.34
133.79


TGA (N2)


 1% Wt. Loss
328
340
359
321
336
350
295
320
320
332


(° C.)


 5% Wt. Loss
358
370
383
353
367
373
343
359
359
360


(° C.)


10% Wt. Loss
370
380
391
366
378
383
361
373
371
370


(° C.)


50% Wt. Loss
403
412
419
399
413
413
400
408
401
402


(° C.)


Thermal HBr
309
127
82
226
<50
256
265
269
72
<50


300° C. (ppm)


GPC


Mw
3740
3700
3400
3689
4093
4232
4080
4070
14000
7900


Mn
3100
2990
2710
2778
3104
3107
1970
1800
8100
3800


Mz
4810
4780
4030
5135
5737
6206
6831
7049
20642
12131


PD
1.2
1.24
1.25
1.33
1.32
1.362
2.07
2.26
1.74
2.08


Color



5.71


(YI Powder)


Color (solution)


L
100.29
99.27
98.82
99.29
99.6
N/A
99.15
99.34
98.58
98.1


a
−0.28
−0.42
−0.65
−0.23
−0.54
N/A
−2.15
−2.08
−1.07
−1.88


b
1.83
2.87
3.64
2.95
2.81
N/A
6.47
6.06
5.2
7.69


ΔE
1.87
2.99
3.88
3.04
2.89
N/A
6.87
6.44
5.50
8.14









HIPS and ABS Formulations

General Procedure for Compounding, Injection Molding and Testing of HIPS and ABS Formulated with CLASP Materials.
HIPS
The HIPS resin and the flame-retardant in addition to antimony oxide were mixed in a plastic bag using a tumble mixer for approximately 10 minutes prior to extrusion. The compounding was conducted on a Werner & Pfleiderer ZSK30 twin-screw extruder at 175 rpm. The feed rate was 8 kg/hr. The temperature profile was 175-175-190-215-215° C. In some cases, the first zone temperature was lowered to 125-150° C. in order to avoid sticking issues at feed throat. A trap was used to capture any volatiles if there was any. The extruded strand was first cooled down by passing an iced-water bath and then pelletized on-line. All formulations were injection molded at a Battenfeld BA350 CD injection-molding machine. The temperature profile was 195-195-205° C. for most of the samples. A lower feed zone temperature of 190° C. was used in some cases. The mold temperature was 40° C.
ABS
The ABS resin, flame-retardant, antimony oxide and antioxidant were mixed in a plastic bag using a tumble mixer for approximately 10 minutes prior to extrusion. The compounding was conducted on a Werner & Pfleiderer ZSK30 twin-screw extruder at 175 rpm. The feed rate was 8 kg/hr. The temperature profile was 190-210-210-220-220° C. In some cases, the first zone temperature was lowered to 125-150° C. in order to avoid sticking issues at feed throat. A trap was used to capture any volatiles if there was any. The extruded strand was first cooled down by passing an iced-water bath and then pelletized on-line. All formulations were injection molded at a Battenfeld BA350 CD injection-molding machine. The temperature profile was 204-216-221° C. The mold temperature was 40° C.
Testing was performed on HIPS and ABS samples according to the following ASTM test standards: VICAT (ASTM D649); Heat Deflection Temperature under Load (ASTM D648) 1⁄8′′ (32 mm) at 264 psi; Notched-Izod Impact Strength (ASTM D256 method A); and Melt Flow Index (ASTM D1238 procedure A), 200° C./5 kg. The UL-94 flammability test was performed on 1⁄8′′ (32 mm) bars. The results are reported in Table II.



















HIPS FORMULATION
1
2
3
4
5
6
7



















Bromination


1
2
3
4
5
7
8


Example











Dow 801 

wt. %
81.1
82.2
82.5
83.2
83.3
82.3
82.5


(HIPS)











Brightsun HB 

wt. %
4.0
4.0
4
4
4
4
4


(ATO)











Br-FR Loading

wt. %
14.9
13.8
13.5
12.8
12.7
13.7
13.5


PROPERTIES











HDT, 264 psi
ASTM
° C.
68.4
70.8
69.3
73.0
73.0
68.4
69.3



D648










Vicat
ASTM
° C.


96.1
100
99.9
94.7
95.8



D649










Izod Impact
ASTM
ft-lb/in
1.44
1.34
1.36
1.48
1.51
1.34
1.36



D256










UL-94, 1⁄8′′
UL-94
rating
fail
V-0
V-0
V-0
V-0
V-0
V-0





(time)








MFI, 200° C./
ASTM
g/10
17.1
18.2
14.3
11.3
10.9
15.2
14.5


5 kg
D1238
min
















HIPS FORMULATION
8
9
10
11
12
13


















Bromination


10
11
12
13
14
15


Example










Dow 801 

wt. %
81.9
82.5
82.6
81.4
82.0
82.5


(HIPS)










Brightsun HB 

wt. %
4.0
4.0
4.0
4.0
4.0
4


(ATO)










Br-FR Loading

wt. %
14.1
13.5
13.4
14.6
14.0
13.5


PROPERTIES










HDT, 264 psi
ASTM
° C.
70.6
73.2
73.4
72.3
73.4
71.9



D648









Vicat
ASTM
° C.
93.9
96.4
97.4
96.6
98
99.4



D649









Izod Impact
ASTM
ft-lb/in
1.36
1.42
1.42
1.30
1.33
1.33



D256









UL-94, 1⁄8′′
UL-94
rating
V-0
V-0
V-0
V-0
V-0
V-0


MFI, 200° C./
ASTM
g/10
15.53
13.5
12.61
14.53
13.28
11.6


5 kg
D1238
min

















HIPS FORMULATION
14
15
16
17
18
19
20



















Bromination


16
17
18
19
21
22
23


Example











Dow 801

wt. %
82.5
82.0
82.5
82.6
82.1
82.5
82.8


(HIPS)











Brightsun HB 

wt. %
4
4
4
4
4
4
4


(ATO)











Br-FR Loading

wt. %
13.5
14.0
13.5
13.4
13.9
13.5
13.2


PROPERTIES











HDT, 264 psi
ASTM
° C.
73.1
72.2
72.4
72.9
72.5
73.5
74.1



D648










Vicat
ASTM
° C.

99.4
100.7
100.8
99.9
101
101.2



D649










Izod Impact
ASTM
ft-lb/in
1.36
1.37
1.42
1.42
1.44
1.46
1.51



D256










UL-94, 1⁄8′′
UL-94
rating
V-0
V-0
V-0
V-0
V-1
V-0
V-0


MFI, 200° C./
ASTM
g/10
12.7
12.1
10.3
10.1
11.5
10.4
9.1


5 kg
D1238
min

















HIPS FORMULATION
21
22
23
24
25
26
27



















Bromination


24
25
26
27
28
29
30


Example











Dow 801

wt. %
82.0
82.5
82.8
82.3
82.6
81.4
81.4


(HIPS)











Brightsun HB 

wt. %
4
4
4
4
4
4
4


(ATO)











Br-FR Loading

wt. %
14.0
13.5
13.2
13.7
13.4
14.6
14.6


PROPERTIES











HDT, 264 psi
ASTM
° C.
72.9
73.4
74.5
73.2
74
74.8
73.5



D648










Vicat
ASTM
° C.
99.8
100.9
101.2







D649










Izod Impact
ASTM
ft-lb/in
1.31
1.39
1.46
1.27
1.38
0.92
0.86



D256










UL-94, 1⁄8′′
UL-94
rating
V-0
V-0
V-0
V-0
Fail*
V-0
V-0


MFI, 200° C./
ASTM
g/10
11.9
10.1
9.0
11.3
10.1
8.8
11


5 kg
D1238
min
























ABS FORMULATION
1
2
3
4
5
6
7



















Bromination


3
4
5
6
7
10
11


Example











Dow 342 EZ

wt. %
79.2
80.0
80.1
79.4
78.8
78.3
79.1


Brightsun HB 

wt. %
4.5
4.5
4.5
4.5
4.5
4.5
4.5


(ATO)











AT-181

wt. %
0.1
0.1
0.1
0.1
0.1
0.1
0.1


Br-FR Loading

wt. %
16.2
15.4
15.3
16.0
16.6
17.1
16.3


PROPERTIES











HDT, 264 psi
ASTM
° C.
72.4
73.9
74.2
72.6
71.2
71.7
73.5



D648










Vicat
ASTM
° C.
99.8
103.2
103
100.4
98.9





D649










Izod Impact
ASTM
ft-lb/in
1.76
1.80
1.86
1.87
1.78
1.77
1.88



D256










UL-94, 1⁄8′′
UL-94
rating
V-0
V-0
V-0
V-0
V-0
V-0
V-0


MFI, 230° C./
ASTM
g/10
11.6
10.1
10.2
11.0
11.8
11.9
11.2


3.8 kg
D1238
min





















ABS FORMULATION
8
9
10
11
















Bromination


12
13
14
15


Example








Dow 342 EZ

wt. %
79.4
77.9
78.5
79.2


Brightsun HB 

wt. %
4.5
4.5
4.5
4.5


(ATO)








AT-181

wt. %
0.1
0.1
0.1
0.1


Br-FR Loading

wt. %
16.0
17.5
16.9
16.2


PROPERTIES








HDT, 264 psi
ASTM
° C.
74.4
73.9
74.4
73.4



D648







Vicat
ASTM
° C.



102.2



D649







Izod Impact
ASTM
ft-lb/in
1.88
1.64
1.77
1.76



D256







UL-94, 1⁄8′′
UL-94
rating
V-0
V-0
V-0
V-0


MFI, 230° C./
ASTM
g/10
10.0
11.7
11.9
10.0


3.8 kg
D1238
min

















ABS FORMULATION
12
13
14
15
16
17
18



















Bromination


16
17
18
19
21
22
23


Example











Dow 342 EZ 

wt. %
79.4
78.6
79.2
79.3
78.7
79.2
79.6


Brightsun HB 

wt. %
4.5
4.5
4.5
4.5
4.5
4.5
4.5


(ATO)











AT-181

wt. %
0.1
0.1
0.1
0.1
0.1
0.1
0.1


Br-FR Loading

wt. %
16.0
16.8
16.2
16.1
16.7
16.2
15.8


PROPERTIES











HDT, 264 psi 
ASTM
° C.
73.9
74
74.8
75.8
73.9
75.4
76.8



D648










Vicat
ASTM
° C.
101.9
102.3
103.6
103.7
102.2
103.4
103.9



D649










Izod Impact
ASTM
ft-lb/in
1.73
1.71
1.75
1.78
1.67
1.71
1.70



D256










UL-94, 1⁄8′′
UL-94
rating
V-0
V-0
V-0
V-0
V-0
V-0
V-0


MFI, 230° C./
ASTM
g/10
10.3
11.3
10.7
10.0
11.5
10.3
10.3


3.8 kg
D1238
min















ABS FORMULATION
19
20
21
22
23

















Bromination


24
25
26
27
28


Example









Dow 342 EZ 

wt. %
78.6
79.2
79.6
79.0
79.3


Brightsun HB 

wt. %
4.5
4.5
4.5
4.5
4.5


(ATO)









AT-181

wt. %
0.1
0.1
0.1
0.1
0.1


Br-FR Loading

wt. %
16.8
16.2
15.8
16.4
16.1


PROPERTIES









HDT, 264 psi 
ASTM
° C.
74.4
76
76.1
74.8
75.2



D648








Vicat
ASTM
° C.
102.9
103.8
104.1
102.7
103.2



D649








Izod Impact
ASTM
ft-lb/in
1.58
1.63
1.68
1.66
1.76



D256








UL-94, 1⁄8′′
UL-94
rating
V-0
V-0
V-0
V-0
V-0


MFI, 230° C./
ASTM
g/10
10.6
10.1
9.1
10.5
10.2


3.8 kg
D1238
min





*fail due to after glow

## Claims

1. A flame retardant composition comprising a brominated polymer distribution having a brominated monoadduct content, where said brominated monoadduct content does not exceed about 25 GPC area %, wherein the composition: (i) contains above 72 wt % bromine; and (ii) contains less than about 1,000 ppm (weight/weight) thermally labile Br as determined by the Thermally Labile Bromine Test, the wt % and ppm values being based upon the total weight of the composition, wherein said polymer distribution is an anionic, chain transfer, vinyl aromatic polymer (ACTVAP) distribution having a chain length distribution of individual polymer constituents prior to bromination having the general formula:


Ar—CRH[—CH2CH(Ar)]n-CH2CH2—Ar,


wherein Ar is a phenyl group, R is a C1-C4 alkyl group or hydrogen and n is the number of repeating monomer units; wherein each phenyl group in the brominated polymer distribution contains from about 2 to about 5 bromine substituents per phenyl group on an individual, not average, basis, wherein the brominated ACTVAP distribution comprises at least about 97 wt % of the total weight of the flame retardant composition, with the remainder being by-product impurities, wherein the Tg value of the brominated composition is within the range of from about 35° C. to about 165° C.; and wherein the composition GPC Mw is in the range of from about 1250 to about 14,000 Daltons, and GPC Mn is in the range of from about 1070 to about 8,200 Daltons and a PD less than about 2.2.

2. The composition of claim 1 wherein the composition has a TGA 5 wt % loss at a temperature of from about 280° C. to about 380° C. under nitrogen.

3. The composition of claim 1 wherein the brominated ACTVAP distribution comprises from about 99 to about 99.95 wt % of the total composition weight, with the remainder being by-product impurities.

4. The composition of claim 1 wherein the brominated monoadduct content of said composition does not exceed about 10 wt %, based on the total weight of the composition.

5. The composition of claim 1 wherein the composition has a Yellowness Index (ASTM D1925) within the range of from about 1 to about 8.

6. The composition of claim 1 wherein the brominated ACTVAP molecular weight distribution is a brominated anionic, chain transfer, styrene polymer (ACTSP) distribution said polymer prior to bromination having the formula C6H5—CH2[—CH2CH(C6H5)]n-CH2CH2—C6H5, wherein n is the number of repeating units.

7. The composition of claim 6 wherein the composition has a TGA wt % loss of 5% at a temperature of from about 290 to about 380° C.

8. The composition of claim 6 wherein the brominated ACTSP distribution comprises from about 99 to about 99.95 wt % of the total composition weight, with the remainder being by-product impurities.

9. The composition of claim 6 wherein the composition has a Yellowness Index (ASTM D1925) of from about 1 to about 8.

10. The composition of claim 6 wherein the composition has a glass transition temperature within the range of from about 70° C. to about 160° C.

11. A HIPS-based formulation containing a flame retardant amount of the composition of claim 1 or 6, and optionally a flame retardant synergist.

12. An ABS-based formulation containing a flame retardant amount of the composition of claim 1 or 6, and optionally a flame retardant synergist.

13. A HIPS-based formulation or an ABS-based formulation containing a flame retardant amount of the composition of claim 1 or 6, said flame retardant amount being within the range of from about 3 to about 25 wt % based on the total weight of the formulation.

14. A formulation of claim 13 wherein the formulation additionally contains a synergistic amount of a flame retardant synergist, said synergistic amount being in the range of up to about 12 wt %.

15. A flame retardant composition comprising a brominated polymer (ACTVAP) distribution having a brominated monoadduct content, where said brominated monoadduct content does not exceed about 25 GPC area %, wherein the composition: (i) has a glass transition temperature (Tg) within the range of from about 75° C. to about 135° C.; (ii) contains above 72 wt % bromine; and (iii) contains less than about 1,000 ppm (weight/weight) thermally labile Br as determined by the Thermally Labile Bromine Test; the wt % and ppm values being based upon the total weight of the composition, wherein said polymer distribution is an anionic, chain transfer, vinyl aromatic polymer (ACTVAP) distribution having a chain length distribution of individual polymer constituents prior to bromination of the general formula:


Ar—CRH[—CH2CH(Ar)]n-CH2CH2—Ar,


wherein Ar is a phenyl group, R is a C1-C4 alkyl group or hydrogen and n is the number of repeating monomer units; wherein each phenyl group in the brominated polymer distribution contains from about 2 to about 5 bromine substituents per phenyl group on an individual, not average, basis; wherein the brominated ACTVAP distribution comprises at least about 97 wt % of the total weight of the flame retardant composition, with the remainder being by-product impurities, and wherein the composition GPC Mw is in the range of from about 1250 to about 14,000 Daltons, and GPC Mn is in the range of from about 1070 to about 8,200 Daltons and a PD less than about 2.2.

16. The composition of claim 15 wherein the composition has a TGA 5 wt % loss at a temperature of from about 290° C. to about 380° C.

17. The composition of claim 15 wherein the brominated ACTVAP distribution comprises from about 99 to about 99.95 wt % of the total composition weight, with the remainder being by-product impurities.

18. The composition of claim 15 wherein the brominated monoadduct content of said composition does not exceed about 5 wt %, based on the total weight of the composition.

19. The composition of claim 15 wherein the composition has a Yellowness Index (ASTM D1925) within the range of from about 1 to about 8.

20. The composition of claim 15 wherein the brominated ACTVAP molecular weight distribution is a brominated anionic, chain transfer, styrene polymer (ACTSP) distribution, said polymer prior to bromination having the formula C6H5—CH2[—CH2CH(C6H5)]n-CH2CH2—C6H5, wherein n is the number of repeating units.

21. The composition of claim 20 wherein the composition has a TGA wt % loss of 5% at a temperature of from about 290° C. to about 380° C.

22. The composition of claim 20 wherein the brominated ACTSP distribution comprises from about 99 to about 99.95 wt % of the total composition weight, with the remainder being by-product impurities.

23. The composition of claim 20 wherein the composition has a Yellowness Index (ASTM D1925) of from about 1 to about 8.

24. The composition of claim 20 wherein the brominated monoadduct content of said composition does not exceed about 1 wt % based on the total weight of the composition.

25. A HIPS-based formulation containing a flame retardant amount of the composition of claim 15 or 20.

26. An ABS-based formulation containing a flame retardant amount of the composition of claim 15 or 20.

27. A composition as claimed in any of claim 1, 6, 15, or 20 wherein the composition contains about 500 ppm or less of thermally labile Br.

28. A thermoplastic article containing any of the compositions of claim 1, 6, 15 or 20.