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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0066—Flame-proofing or flame-retarding additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F112/02—Monomers containing only one unsaturated aliphatic radical
  • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F112/06—Hydrocarbons
  • C08F112/08—Styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
  • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F12/06—Hydrocarbons
  • C08F12/08—Styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/18—Introducing halogen atoms or halogen-containing groups
  • C08F8/20—Halogenation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/18—Introducing halogen atoms or halogen-containing groups
  • C08F8/20—Halogenation
  • C08F8/22—Halogenation by reaction with free halogens
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/14—Macromolecular materials
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

• This invention relates to certain novel and especially useful brominated flame retardants and novel hydrocarbon precursors of such flame retardants, the preparation of all such materials and the use of the brominated materials as flame retardants.
• Styrene is a readily available starting material and can be polymerized to form telomeric, oligomeric and low molecular weight polymeric distributions of polystyrene chains.
• Such polymerization reactions include radical, cationic and anionic mechanisms with and without chain transfer.
• M n can be calculated from polydispersity but unfortunately the value of M z was not reported in either paper for any of the distributions; in as much as APS chemistry is well known to produce near Gaussian shaped distributions. Hence M n and M z are symmetrically displaced about the central tendency or mean M w and M z does not deviate significantly from M w .
• TSTD materials suffered from increased asymmetry reflected by broader distributions and significant skewness.
• a typical distribution is represented in Fig. 2. Note, the sequentially decreasing relative weight percent with increasing molecular weight of each individual telomer chain in the distribution shown in Fig. 2.
• the material has a degree of polymerization of about 8, it has very significant levels (e.g., greater than about 25 wt%) of component telomer chains with molecular weights in excess of 2,000 molecular weight and still significant levels (e.g., greater than about 2.5 wt%) of component telomer chains with molecular weights in excess of 5,000 molecular weight, hence such a distribution loses the advantages gained from having short chain lengths and the ability to be brominated at levels in excess of 71 wt% bromine, cleanly and free of chain cleavage side reactions.
• TGA thermogravimetric analysis
• novel brominated aromatic hydrocarbon polymers of this invention have broad spectrum flame retardant characteristics in that they are effective in a variety of host polymers to be flame retarded and the resultant polymer blends exhibit desirable thermal, impact, rheological, and color properties.
• This invention also provides novel toluene styrenic telomer distributions uniquely suited for formation of brominated styrenic polymers having high bromine content and a unique combination of advantageous properties. Such properties are the result of the unique shape, breadth, limited skewness, and low asymmetry values characteristic of the unbrominated toluene styrenic telomers of this invention.
• this invention provides new polymer compositions in which the flame retardant compositions of this invention have been blended.
• Fig. 1 is a bar graph representing the relative distribution of weight fractions as a function of the molecular weight of the discrete component chains of a prior art anionic polystyrene benzyl oligostyrene distribution having a molecular weight of 710 Daltons.
• Fig. 2 is a bar graph representing the relative distribution of weight fractions as a function of the molecular weight of the discrete component chains of a Weibull distribution formed from an anionic chain transfer styrene telomer reaction akin to the EP 0 741 147 Al, Example 1.
• Fig. 3 is a bar graph representing the relative distribution of weight fractions as a function of the molecular weight of the discrete component chains of a Lognormal distribution formed from an anionic chain transfer styrene telomer reaction akin to EP 0 741 147 Al, Example 4.
• Fig. 4 is a bar graph representing the relative distribution of weight fractions as a function of the molecular weight of the discrete component chains of a toluene styrenic telomer distribution described by a Weibull distribution and formed by process technology of this invention.
• Fig. 3 is a bar graph representing the relative distribution of weight fractions as a function of the molecular weight of the discrete component chains of a Lognormal distribution formed from an anionic chain transfer styrene telomer reaction akin to EP 0 741 147 Al, Example 4.
• Fig. 4 is a bar graph representing the relative distribution of weight fractions as a function of the molecular weight of the discrete component chains of
• Fig. 5 is a bar graph representing the relative distribution of weight fractions as a function of the molecular weight of the discrete component chains of a toluene styrenic telomer distribution described by Beta distribution and formed by process technology of this invention.
• Fig. 6 is a graphical depiction of the relationship of the melt flow index of high impact polystyrene resin compositions formed from brominated styrenic polymers of this invention and the glass transition temperatures of said brominated styrenic polymers used.
• Fig. 6 is a graphical depiction of the relationship of the melt flow index of high impact polystyrene resin compositions formed from brominated styrenic polymers of this invention and the glass transition temperatures of said brominated styrenic polymers used.
• Fig. 7 is a graphical depiction of the relationship of the Vicat of high impact polystyrene resin compositions formed from brominated styrenic polymers of this invention and the glass transition temperatures of said brominated styrenic polymers used.
• Fig. 8 is a graphical depiction of the relationship of the dependency of glass transition temperature of brominated styrenic polymers of this invention on molecular weight as specified as M w of unbrominated STSTDs of this invention from which the brominated styrenic polymers were formed.
• Fig. 8 is a graphical depiction of the relationship of the dependency of glass transition temperature of brominated styrenic polymers of this invention on molecular weight as specified as M w of unbrominated STSTDs of this invention from which the brominated styrenic polymers were formed.
• YI Hunter Color Yellowness Index
• compositions which comprise telomer distributions in which styrene is the taxogen (polymerizable reagent) and toluene is the telogen (chain transfer agent) which is telomerized in the anionic chain transfer styrene reaction.
• taxogen polymerizable reagent
• telogen chain transfer agent
• n is an average number in the range of about 1.5 to about 5.5 with the proviso that 1,3- diphenylpropane, a compound of the above formula in which n is 0, optionally is present in said distribution in an amount of not more than 25 GPC area %, and wherein said distribution is further characterized by having an M w in the range of about 430 to about 1000, an M n in the range of about 350 to about 770, an M z in the range of about 550 to about 1700, a polydispersity in the range of about 1.2 to about 1.65, a standard deviation in the range of about 160 to about 500, and an asymmetry in the range of about 1.3 to about 3.2.
• a composition is provided, which comprises a distribution of toluene st
• a composition which comprises a distribution of toluene styrenic telomers of the formula: (I) C6H5CH 2 CH 2 -[(C6H5)CHCH 2 -] n CH 2 C ⁇ H5 wherein each C 6 Hs is a phenyl group and for each molecule of said formula, n is an average number in the range of about 2.9 to about 3.9 with the proviso that 1,3- diphenylpropane, a compound of the above formula in which n is 0, optionally is present in said distribution in an amount of not more than 1 GPC area %, and with the further proviso that said distribution optionally further contains toluene in an amount of not more than 0.1 wt%, and wherein said distribution is further characterized by having an M w in the range of about 650 to about 750, an M n in the range of about 500 to about 600, an M z in the range of about 830 to about 1120, and a polydispers
• the distributions of the compositions described in this paragraph are further characterized by having an M w in the range of about 690 to about 730, an M n in the range of about 520 to about 560, an M z in the range of about 910 to about 960, and a polydispersity in the range of about 1.25 to about 1.32.
• Particularly preferred embodiments of this invention are ACTSRs that yield TSTDs which can be reasonably described (modeled) by both equation (1) below. Equation (1) is known as the Weibull probability density function (PDF). Equation (1) is evaluated for discrete values of X 1 . Such a typical Weibull distribution is represented by Fig. 4.
• Equation (2) provides the normalized weight fraction X] for telomer component chain X 1 .
• M n , M w and M z are calculated from the Weibull distribution, according to the equations for those parameters presented in Table 2 above.
• n, X 1 M 1 (3)
• Preferred TSTDs for forming polymeric brominated flame retardants have M n in the range of about 425 to about 600, M w in the range of about 580 to about 960, M 2 . in the range of 760 to about
• ACTSR compositions that yield toluene styrenic telomer distributions, TSTDs which have relatively low 1,3- diphenylpropane content.
• TSTDs can be reasonably described (modeled) by both equation (4) below. Similar to the discussion above regarding Weibull distributions, equation (4) below is known as the Beta probability density function. Equation (4) below can be evaluated for discrete values of polymer component chain X 1 . However it is more convenient to use the cumulative Beta distribution equation (5) below which, like the Weibull PDF, is generally provided as a function of modern spread sheet software programs. Such a typical Beta distribution is represented by Fig. 5.
• values for M n , M w and M z are calculated but now from the difference in the cumulative Beta probability density function evaluated at discrete values of X 1 and X 1 .] according to equation (6) below.
• Beta distributions are formed. Beta distributions result from process conditions of this invention that entail the presence of a co-catalyst such as a metal alkoxide.
• a Beta distribution is characterized by the fact that it is a probability density of the random variable x, where the population of x is dictated by a second random event enacted upon the population established by the first random event.
• the first random event is chain transfer from the chain transfer agent toluene.
• the probability of chain transfer from the chain transfer agent toluene is denoted as P 11 .
• Beta toluene styrenic telomer distributions of this invention would indicate that P rl » P r2 » P r3 > • • -P n -
• One skilled in the art would recognize that the trend is easily rationalized based on size, steric interactions (chain entanglements) and rates of diffusion of smaller size component chains.
• One surprising attribute of the Beta distributions formed using a metal alkoxide cocatalyst is that these distributions when formed in a metal reactor, such as a 316 stainless steel reactor, do not exhibit reduced thermal color stability at 300 0 C when brominated as compared to Weibull distributions formed without the cocatalyst in such metal reactor.
• compositions which comprise in the range of about 0.1 to about 99.9 wt% of a composition of i), ii), iii), or iv) and in the range of about 99.9 to about 0.1 wt% of one or more styrene based telomer distribution(s) formed from one or more aromatic hydrocarbon compounds having in the range of about 1 to about 4 aromatic rings in the molecule (which may be condensed or non-condensed or a combination of condensed and non- condensed), and which compounds are further characterized in that (a) when the compound has 1 to about 4 aromatic rings in the molecule the substituent or the substituents on the ring(s) consist(s) of two or more methyl group(s) per molecule, or (b) when the compound has 2 to about 4 aromatic rings in the molecule the sole substituent on the ring(s) of the compound is a single methyl group.
• each x is the same or different and is a whole number in the range principally of 2 to 5 (it is conceivable that very small fractions of rings exist where x is 0 or 1);
• Fresh toluene 40 pounds, (197 mol) and 97.3 Ib of recycled toluene (containing 97.1%, 94.5 Ib, 465 mol toluene; 1.7%, 1.6 Ib, 6.2 mol TMEDA; 0.3%, 0.3 Ib, 0.7 mol, 1,3-diphenlypropane; 0.9%, 0.9 Ib, 4.9 mol cyclohexane) was charged to the reactor; Karl Fischer moisture analysis indicated 7 ppm residual H 2 O. Agitation began. The solvent was heated to 79° C by applying tempered water to the vessel jacket.
• Example 10 The procedure of Example 10 was repeated except that: 1437 g ( ⁇ 1.7 liters, 15.60 mole) of toluene was charged to the reactor (49 ppm residual H 2 O), which was further made anhydrous by the addition of 0.36 g (5.6 mmole) n-butyllithium.
• the anhydrous toluene was heated to 8O 0 C, upon reaching the set point temperature, 52.60 g n- butyllithium solution (2.0 M, 16.5 wt% in cyclohexane, 0.135 mole) was charged through the charge vessel and delivered subsurface to the gently agitated (300 rpm) toluene solution.
• TSTDl 3 Forming Toluene Styrenic Telomer Distribution
• the vessel and line were flushed with a 100 ml aliquot of toluene before charging with 47.74 g n-butyllithium solution (2.0 M, 16.5 wt% in cyclohexane, 0.123 mole). All total (the initial charge, the amount used to form the potassium t-butoxide/TMEDA solution and the amount used to flush the charge lines) 1598 g (17.3 mole) of toluene was charged to the reactor prior to initiating the styrene feed.
• the quench is conveniently performed at ambient temperature and generally speaking no heating other than the heat of solution of residual HBr is needed to effect a phase separation. Since bromine and other active brominating species can be present it is preferred to minimize heating of the mixture and to limit exposure to visible light. This assists, to some extent, in helping to ensure a low thermally labile bromine content.
• hydrazine hydrate is added to the quenching wash water to immediately treat unreacted bromine. Hydrazine may even attenuate the activity of other active bromine species if present.
• brominated flame retardants of this invention are characterized, among other things, by being broad spectrum flame retardants. This means that the flame retardants can be effectively used in a wide variety of different types of polymers, including various thermoplastic polymers. Additionally, the brominated flame retardants of this invention are deemed to be effective in thermoset polymers, such as epoxy resins used for printed wiring and circuit boards, as well as natural and synthetic elastomers, including thermoplastic polyurethane elastomers (TPU), etc.
• TPU thermoplastic polyurethane elastomers

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