Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/22—General preparatory processes using carbonyl halides
  • C08G64/24—General preparatory processes using carbonyl halides and phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
  • C08G64/307—General preparatory processes using carbonates and phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/04—Aromatic polycarbonates
  • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
  • C08G64/14—Aromatic polycarbonates not containing aliphatic unsaturation containing a chain-terminating or -crosslinking agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates

Definitions

• This disclosure relates to a process for the production of branched polycarbonates.
• Aromatic polycarbonates are used in a variety of applications due to their excellent mechanical and physical properties including, among others, impact and heat resistance, strength and transparency.
• the third general process, a "non-phosgene" melt process as shown in Figure 3 was developed to eliminate the use of highly toxic phosgene in the process flow.
• non-phosgene melt process shown (also referred to as the melt transesterification process) is preferred since it prepares polycarbonates less expensively and with better optical properties than the interfacial process and avoids the use of highly toxic phosgene.
• Both types of melt processes make use of a diarylcarbonate, such as diphenylcarbonate as an intermediate, which is polymerized with a dihydric phenol such as bisphenol A in the presence of an alkaline catalyst to form a polycarbonate in accordance with the general reaction scheme shown in Figure 4.
• This polycarbonate may be extruded or otherwise processed, and may be combined with additives such as dyes and UV stabilizers.
• branched polycarbonate with high melt strength.
• blow molding of bottles and extrusion of sheet products from polycarbonate requires the polycarbonate to have high melt strength.
• branched polycarbonate resins can be used in extrusion processes for the production of profiles, solid sheets, multi-wall sheets or corrugated sheets.
• DE 1570533 to Fritz et al. discloses a method for making branched polycarbonate by adding 0.25 to 1.5 mole percentage (with respect to the bisphenol) of a phenol with a functionality higher than 2.
• the example of DE- 1570533 teaches the use of 4,6-dimethyl-2, 4, 6-tri-(4-hydroxyphenyl)-2-heptene or trimeric isopropenyl phenol. It should be noted, however, that the use of branching agents having benzylic hydrogens and double bonds like trimeric isopropenyl phenol lead to the development of discoloration in melt processed polycarbonates.
• DE 19727709 to Bunzar et al. discloses a method for making branched melt polycarbonate using 3 to 6 functional aliphatic alcohols.
• the examples of DE 19727709 teach a method of polymerizing the branching agents pentaerythritol or dipentaerythritol directly together with the monomers Bisphenol A and diphenyl carbonate.
• the use of aliphatic alcoholic monomers instead of aromatic phenolic monomers leads to reductions in reaction rates during melt polymerization, lower thermal stability and discoloration in the resulting polymer.
• US 5693722 to Priddy Jr. et al. discloses a method for making a branched polycarbonate by first synthesizing a polycyclic-oligocarbonate and then melt-mixing the polycyclic-oligocarbonate together with a polycarbonate resin.
• This multi-step process requires separate and complicated reaction systems for preparing each of the two reactants, the polycyclic oligocarbonate and the polycarbonate, and for the subsequent reaction.
• polycyclic-oligocarbonates are prepared from chloroformates in solution, and as a result the melt polycarbonates contain residual solvents and chlorinated compounds, both of which characteristics are undesirable in terms of handling, environmental, and product quality standpoints.
• a process for the production of branched aromatic polycarbonates that includes reacting a diarylcarbonate and a polyhydric alcohol in the presence of an alkaline catalyst to produce a polycarbonate oligomer; adding a branching agent to the polycarbonate oligomer, wherein the branching agent has the formula (I):
• A is a C ⁇ - 20 polymethylene, C 2 - 2 o alkylene or alkylidene, C 5 . 36 cycloalkylene or cycloalkylidene, C 6 . 36 arylene or alkylarylene, or C 6 . 36 arylalkylene, wherein G is a monovalent C 6 -C 30 hydrocarbon having at least one hydroxyl group bonded directly to an aromatic or cycloaliphatic ring and y is an integer greater than 2, and wherein each G may be the same or different; and producing a branched aromatic polycarbonate having a melt index ratio greater than that of an aromatic polycarbonate produced from the polycarbonate oligomer without the addition of the branching agent.
• the branching agent is added in combination with a carbonic acid diester to a polycarbonate oligomer produced during the polymerization of polycarbonate.
• the carbonic acid diester comprises a compound selected from the group consisting of compounds having formula (IV): o
• R] and R 2 may be the same or different and are selected from the group consisting of phenyl, C 6 - 2 o aryl, C 6 - 20 arylalkyl groups, and wherein Ri and R 2 may optionally be substituted with activating groups.
• Figure 1 illustrates an interfacial process for the production of polycarbonate
• Figure 2 illustrates a phosgene-based melt process for the production of polycarbonate
• Figure 3 illustrates a non-phosgene melt process for the production of polycarbonate
• Figure 4 illustrates a prior art process carried out in a base-catalyzed melt polycondensation reaction.
• a process for preparing branched polycarbonates generally includes adding a branching agent to a polycarbonate oligomer formed during a process for the production of a finished polycarbonate.
• the branching agent is added to the polycarbonate oligomer in combination with a carbonic acid diester compound.
• Applicants have su ⁇ risingly found that upon adding the branching agent to the polycarbonate oligomer, individually or in combination with the carbonic acid diester, the branching agent can be rapidly inco ⁇ orated into the polycarbonate for a controlled build-up of melt strength. Moreover, it has been found that adding the branching agent to the polycarbonate oligomer, individually or in combination with the carbonic acid diester, simplifies the transition and recovery of reaction byproducts and monomers in continuous reaction systems.
• the branching agent preferably has the general structure as shown in formula (I):
• A is a C ⁇ - 20 polymethylene, C 2 - 0 alkylene or alkylidene, C 5 - 36 cycloalkylene or cycloalkylidene, C 6 - 36 arylene or alkylarylene, or C 6 - 36 arylalkylene.
• A is optionally substituted with additional hydroxyl groups.
• G is a monovalent C 6 -C 3 o hydrocarbon having at least one hydroxyl group bonded directly to an aromatic or cycloaliphatic ring and y is an integer greater than 2, wherein each G may be the same or different.
• G comprises the following formula (II);
• G comprises the following formula (III):
• R] of formulas (II) and (III) is a hydrogen, Cj- 8 alkyl, C 6 - 2 o aryl, or C 6 - o arylalkyl, and all Ri can be the same or different.
• the structure of the branching agent is free of benzylic hydrogens, the presence of which has been detemiined to undesirably contribute to coloration of the finished branched polycarbonate.
• the branching agent is added in combination with a non-activated carbonic acid diester compound.
• the carbonic acid diester has the general structure as shown by formula (IN): o
• Rj and R 2 may be the same or different and are selected from the group consisting of phenyl, C 6 . 2 o aryl, C 6 - 2 o arylalkyl groups.
• R] and R 2 may optionally be substituted with activating groups.
• the non-activated carbonic acid diester is diphenyl carbonate.
• the carbonic acid diester is an activated diphenyl carbonate with ortho- electron withdrawing groups of the general structure shown in structure (V):
• B is an electronegative substituent and m is an integer from 1 to 5.
• Preferred electronegative substituents include carbonyl containing groups, nitro groups, and halo groups.
• a preferred activated diphenyl carbonate structure is shown in structure (VI).
• R 3 and R may be the same or different and are selected from the group consisting of C]. 8 alkoxy, phenoxy, benzyloxy, C 6 - 2 o aryloxy, phenyl and C 6 - 20 aryl. More preferably, R 3 and R are selected from the group consisting of methoxy, ethoxy, n-propoxy, benzyloxy, phenoxy, and phenyl.
• suitable carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, m-cresyl carbonate, dinaphthyl carbonate, and bis(methylsalicyl) carbonate.
• Suitable processes for the manufacture of polycarbonate to which the branching agent, or the combination of branching agent and carbonic acid diester, is added include an interfacial polycondensation process, a melt transesterification process or the like.
• the polycarbonate manufacturing process reacts an aromatic dihydroxy compound with a compound capable of introducing a carbonate bond.
• the use of the melt transesterification process is most preferred.
• the branching agent is preferably added to the polycarbonate oligomer in an amount of about 0.1 to about 2 mole percent with respect to the polycarbonate oligomer.
• the carbonic acid diester is preferably added in a concentration of about 0.1 up to about 2.5 mole percent with respect to the polycarbonate oligomer; more preferably, the carbonic acid diester is given with a mole ratio between about x/1 and about x/3 with respect to the functionality (x) of the branching agent.
• polycarbonate oligomer includes compositions having structural units of the formula (VII):
• R is an aromatic organic radical and, more preferably, a radical of the formula (VIII):
• each of A and A is a monocyclic divalent aryl radical and Y is a bridging radical having one or two atoms which separate A from A .
• Y is a bridging radical having one or two atoms which separate A from A .
• one atom separates A 1 from A 2 .
• the bridging radical Y 1 can be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene or isopropylidene.
• Suitable polycarbonate oligomers can also be produced by reaction of dihydroxy
• dihydroxy compound includes, for example, bisphenol compounds having the general formula (IX) as follows:
• R a and R b each represent a halogen atom or a monovalent hydrocarbon group and may be the same or different; p and q are each independently integers from 0 to 4; and X a represents one of the groups of formula (X):
• R c and R each independently represent a hydrogen atom or a monovalent linear or cyclic hydrocarbon group and R e is a divalent hydrocarbon group.
• dihydroxy compounds suitable for forming the polycarbonate oligomers include the dihydroxy-substituted aromatic hydrocarbons disclosed by name or formula (generic or specific) in U.S. Patent 4,217,438, which is inco ⁇ orated herein by reference.
• a nonexclusive list of specific examples of the types of bisphenol compounds that may be represented by formula (VI) includes bis(hydroxyaryl) alkanes such as bis(4-hydroxyphenyl)methane; 1,1- bis(4-hydroxyphenyl)ethane; 2,2-bis(4-hydroxyphenyl)propane (also known as bisphenol A); 2,2-bis(4-hydroxyphenyl)butane; 2,2-bis(4-hydroxyphenyl)octane; bis(4-hydroxyphenyl)phenylmethane; 2,2-bis(4-hydroxy- 1 -methylphenyl)propane; l ,l-bis(4-hydroxy-t-butylphenyl) propane; and 2,2-bis(4-hydroxy-3- bromophenyl)propane; bis(hydroxyaryl)cycloalkanes such as l,l-(4- hydroxyphenyl)cyclopentane and 1 , 1 -bis(4-hydroxyphenyl)cyclohexane
• polycarbonates are linear homopolycarbonates that are capable of branching upon addition of the branching agent in accordance with this disclosure.
• the carbonic diester acid component for preparing the oligomers may contain a minor amount, e.g., up to about 50 mole % of a dicarboxylic acid or its ester, such as terephthalic acid or diphenyl isophthalate, to prepare polyester polycarbonates.
• the synthesis of polycarbonates may be conducted in the presence of a catalyst, e.g., to promote the transesterification reaction.
• a catalyst e.g., to promote the transesterification reaction.
• suitable catalysts include quaternary ammonium compounds, quaternary phosphonium compounds, alkali metals and alkaline earth metals, oxides, hydroxides, amide compounds, alcoholates, and phenolates, basic metal oxides such as ZnO, PbO, and Sb 2 O 3 , organotitanium compounds, soluble manganese compounds, nitrogen-containing basic compounds and acetates of calcium, magnesium, zinc, lead, tin, manganese, cadmium, and cobalt, and compound catalyst systems such as a nitrogen-containing basic compound and a boron compound, a combination of a nitrogen-containing basic compound and an alkali (alkaline earth) metal compound, a combination of a nitrogen-containing basic compound, an alkali (alkaline earth) metal compound
• the catalyst is a quaternary ammonium compound or a quaternary phosphonium compound.
• Illlustrative non-limiting examples include tetramethyl ammonium hydroxide, tetramethyl ammonium acetate, tetramethyl ammonium fluoride, tetramethyl ammonium tetraphenyl borate, tetraphenyl phosphonium fluoride, tetraphenyl phosphonium tetraphenyl borate, tetrabutyl phosphonium hydroxide, tetrabutyl phosphonium acetate and dimethyl diphenyl ammonium hydroxide.
• the appropriate level of catalyst will depend in part on how many catalysts are being employed. In general, the total amount of catalyst is usually in the range of about 1 x 10 " to about 1.0 mole per mole of the dihydroxy compound. Optionally, when more than one catalyst is employed, each may be inco ⁇ orated into the melt at a different stage of the reaction.
• Terminators or endcapping agents may also be used during the manufacture of the polycarbonate.
• tem inators include phenol, p-tert-butylphenol, p- cumylphenol, octylphenol, nonylphenol and other endcapping agents well-known in the art.
• a coupling agent (similar to the structures employed with the branching agent) such as a bis-alkylsalicyl carbonate, e.g., bis-methyl or ethyl or propyl salicyl carbonate, bis-phenyl or benzyl salicyl carbonate, bis(2-benzoylphenyl) carbonate, BPA-bis-2-alkoxyphenylcarbonate, BPA-bis-2-aryloxyphenylcarbonate, or BPA-bis-2-benzoylphenylcarbonate may also be added to the polycarbonate oligomer.
• a bis-alkylsalicyl carbonate e.g., bis-methyl or ethyl or propyl salicyl carbonate
• bis-phenyl or benzyl salicyl carbonate bis(2-benzoylphenyl) carbonate
• BPA-bis-2-alkoxyphenylcarbonate bis-bis-2-aryloxyphenylcarbonate
• the process of manufacturing branched polycarbonates generally takes place in a series of reactors.
• the temperature is increased and the pressure is reduced along the reactor train. Since the reaction is an equilibrium reaction, byproduct phenol is continuously removed from the reactors to ensure the desired or targeted molecular weight.
• the reaction preferably occurs at temperatures greater than about 230°C, with about 270°C to about 310°C more preferred.
• the pressure of the reaction is preferably reduced to a pressure less than about 0.8 torr, with about 0.2 to about 0.6 torr more preferred.
• a quencher composition may be added and the mixture is passed through an extmder and pellitized.
• the reaction can be carried out by either a batch mode or a continuous mode.
• the polycarbonate obtained may further contain a heat stabilizer, an ultraviolet absorbent, a mold releasing agent, a colorant, an anti-static agent, a lubricant, an anti- fogging agent, a natural oil, a flame retardant, an anti-oxidant, a synthetic oil, a wax, an organic filler and an inorganic filler, which are generally used in the art.
• the branching agent and if present, the carbonic acid diester may be added to the polycarbonate oligomer at any stage during processing including during the extrasion process to produce branched polycarbonates.
• the branching agent, or the combination of branching agent and carbonic acid diester is added after the polycarbonate oligomer has reached a molecular weight (Mw) greater than 4,000 daltons.
• Mw molecular weight
• the Mw of the final branched polycarbonate resin is at least about 24,000 daltons.
• the branching agent may be added to polycarbonate oligomers containing Fries structures to produce branched polymers with controlled melt strength properties.
• Fries and “Fries structures” denote a repeating unit in the polycarbonate having the formula (XI) or (XII):
• the amount of Fries structures present is less than 2,000 parts per million (ppm), with less than 1,500 ppm more preferred, with less than 1,000 ppm even more preferred and with less than 500 ppm most preferred.
• the branched aromatic polycarbonate may still contain residual amounts of unrecovered phenols, unreacted branching agent and the like.
• the branched polycarbonate contains less than about 500 ppm of unrecovered phenols, less than about 500 ppm of unreacted branching agent and less than about 500 ppm of unreacted carbonic acid diester.
• the extent of branching agent reaction can be favorably increased by melt mixing the branching agent or branching agent and carbonic acid diester with a small amount of basic catalyst (such as tetramethylammonium hydroxide) to produce a higher molecular weight carbonic acid diester of the branching agent which can then be added to the polycarbonate oligomer.
• basic catalyst such as tetramethylammonium hydroxide
• melt strength is the Melt Index Ratio (MIR), i.e., the ratio of Melt Volume Rate (MVR) determined at two different loadings.
• MIR Melt Index Ratio
• the branched polycarbonates produced by any of the embodiments preferably have a melt index ratio (MIR) of greater than about 1.3, with about 1.5 more preferred, with greater than about 1.7 even more preferred and with greater than about 1.8 most preferred. Also preferred is a melt index ratio less than about 4, with less than about 3 more preferred, with less than about 2.75 even more preferred, with less than about 2.6 most preferred.
• MIR value of the final resin is increased by at least 0.04 units relative to that of the polycarbonate oligomer to which the branching agent is added, with greater than 0.4 units even more preferred.
• MIR is based on a measurement of melt volume rates exposed to two different loads (i.e., force) in accordance with an International Standards Organization procedure identified as ISO 1133.
• the melt volume rate (MVR) is generally defined as the amount, in cubic centimeters (cm ), of a thermoplastic resin that can be forced through an orifice of known dimensions when subjected to a known force at an elevated temperature within a given period of time.
• the disclosure is further illustrated by the following non-limiting examples.
• a branching agent or a combination of a branching agent and a carbonic acid diester, was added to a polycarbonate oligomer and its resulting effect on melt behavior was studied.
• the examples further include comparative data for polycarbonate oligomers similarly processed without the addition of the branching agent or a combination of the branching agent and the carbonic acid diester.
• the properties of the polycarbonate oligomer employed, made by a continuous melt transesterification process, are shown in Table 1.
• Mw average weight molecular weight
• Mn average number molecular weight
• GPC gel permeation chromatography
• Melt volume rates (cm 3 / 10 minutes) were carried out using International Standards Organization standard conditions (ISO-1133) for polycarbonate at a temperature of 280 °C and at loads of 2.16 kg or 21.6 kg.
• Table 1 Properties of the different starting polycarbonates.
• polycarbonate oligomers characterized in Table I are obtained at different stages from a continuous reactor, wherein polycarbonate A (low molecular weight) represents the oligomer obtained at the early stages in the continuous reactor process flow.
• Polycarbonate B intermediate molecular weight
• Polycarbonate C high molecular weight is obtained from the continuous reactor at a later stage in the process flow.
• a batch reactor tube was charged with 50 g of polycarbonate oligomer A under nitrogen.
• Polycarbonate oligomer A (without the addition of any branching agent or the addition of the combination of a branching agent and a carbonic acid diester) was then heated to a temperature of 310 °C and stirred for 20 minutes. After the melt mixing stage, a vacuum was applied to the system to a pressure of 0.5 millibar. The reaction was continued for an additional 30 minutes. The finished polycarbonate polymer was then sampled from the reaction tube, the results of which are shown in Table 2.
• the batch reactor tube is charged with 50 grams of polycarbonate oligomer A and 0.25 g (0.816 x 10 "3 mol) 1,1,1-tris (4-hydroxyphenyl)ethane (THPE) and processed as in Example 1.
• Formula (XIII) illustrates the chemical stmcture of THPE.
• Example 3 In this Example, the batch reactor tube was charged with 50 grams of polycarbonate oligomer A, 0.25 g (0.816 x 10 "3 mol) THPE and 0.404 g (1.223 x 10 "3 mol) of methylsalicylcarbonate (MSC) under nitrogen and processed as in Example 1.
• Formula (XIV) illustrates the chemical stmcture of MSC.
• Example 2 the batch reactor tube was charged with 50 grams of polycarbonate oligomer A, 0.25 g (0.816 x 10 "3 mol) THPE and 0.262 g (1.223 x 10 "3 mol) diphenylcarbonate (DPC) under nitrogen and processed as in Example 1.
• Formula (XIN) illustrates the chemical stmcture of DPC.
• the batch reactor tube was charged with 50 grams of polycarbonate oligomer A, (0.589 x 10 "3 mol) 4,4'-[l-[4-[l-(4-hydroxyphenyl)-l- methylethyl]phenyl]ethylidine]bisphenol (TrisP-PA) and 0.189 g (0.883 x 10 "3 mol) DPC under nitrogen and processed as in Example 1.
• Formula (XNI) illustrates the stmcture of TrisP-PA.
• the batch reactor tube was charged with 50 grams of polycarbonate oligomer A, 0.25 g (0.718 x 10 "3 mol) 2,6-Bis[(2-hydroxy-5-methylphenyl)methyl]-4- methylphenol (MethyleneTrisP-CR) and 0.231 g (1.076 x 10 "3 mol) DPC under nitrogen and processed as in Example 1.
• Formula (XNII) illustrates the stmcture of MethyleneTrisP-CR.
• the batch reactor tube was charged with 50 grams of polycarbonate oligomer A, 0.25 g (0.565 x 10 "3 mol) 4,4'-[l-[4-[l-(4-hydroxycyclohexyl)-l- methylethyl]phenyl]ethylidine]biscyclohexanol (9H-TPPA) and 0.181 g (0.847 x 10 "3 mol) DPC under nitrogen and processed as in Example 1.
• Formula (XIX) illustrates the structure of 9H-TPPA.
• Example 2 the batch reactor tube was charged with 50 g of polycarbonate oligomer B under nitrogen (without the addition of any branching agent or the addition of the combination of a branching agent and a carbonic acid diester) and processed as in Example 1.
• Example 2 the batch reactor is charged with 50 g of polycarbonate oligomer B and 0.25 g (0.816 x 10 "3 ) mole THPE under nitrogen and processed as in Example 1.
• Example 2 the batch reactor tube was charged with 50 g of polycarbonate oligomer B, 0.25 g (0.816 x 10 "3 mol) THPE and 0.262 g (1.223 x 10 "3 mol) DPC under nitrogen and processed as in Example 1.
• Example 2 the batch reactor tube was charged with 50 grams polycarbonate oligomer B, 0.25 g (0.816 x 10 "3 mol) THPE and 0.404 g (1.223 x 10 "3 mol) MSC under nitrogen and processed as in Example 1.
• Example 2 the batch reactor is charged with 50 g of polycarbonate oligomer C under nitrogen (without the addition of any branching agent or the addition of the combination of a branching agent and a carbonic acid diester) and processed as in Example 1.
• Example 2 the batch reactor is charged with 50 g of polycarbonate oligomer C and 0.25 g (0.816 x 10 "" mole) THPE under nitrogen and processed as in Example 1.
• Example 2 the batch reactor tube was charged with 50 g of polycarbonate oolliiggoommeerr CC,, 00..2255 gg ((00..881166 xx 1100 “"33 mmooll)) TTHHPPIE and 0.262 g (1.223 x 10 "3 mol) DPC under nitrogen and processed as in Example 1.
• Examples 1, 9, 13 polycarbonate oligomers processed without the addition of a branching agent or a combination of a branching agent and a carbonic acid diester.
• the addition of the branching agent individually or in combination with a carbonic acid diester (Examples 2-8, 10-12, 14-15), increased the MIR compared to processing the polycarbonate oligomers without the branching agent (Examples 1, 9, and 13).
• Individually adding the branching agent to the polycarbonate oligomer produced a branched polycarbonate with an increase in melt strength from about 0.04 to about 0.7 MIR units.
• Adding the branching agent in combination with a carbonic acid diester synergistically increased melt strength by greater than 0.6 to about 1.3 MIR units.
• Comparative examples 16-21 illustrate the effect of the addition of a carbonic acid diester without a branching additive to the polycarbonate oligomer.
• Table 3 shows that the addition of a carbonic acid diester without a branching agent did not affect melt strength properties.
• Table 3 also includes the melt index data for branched polycarbonates produced without the addition of a branching agent or a carbonic acid diester (Comparative Examples, 1, 9, and 13).
• the batch reactor tube was charged with 50 g of polycarbonate oligomer A and 0.262 g (1.223 x 10 " " mol) mol DPC under nitrogen and processed as in Example 1.
• the batch reactor tube was charged with 50 g of polycarbonate oligomer A and 0.404 g (1.223 x 10 " ' mole) MSC under nitrogen and processed as in Example 1.
• Example 18 In this example, the batch reactor is charged with 50 g of polycarbonate oligomer B and 0.262 g (1.223 x 10 "3 mole) DPC under nitrogen and processed as in Example 1.
• the batch reactor is charged with 50 g of polycarbonate oligomer B and 0.404 g (1.223 x 10 "" mole) MSC under nitrogen and processed as in Example 1.
• the batch reactor is charged with 50 g of polycarbonate oligomer C and 0.262 g (1.223 x 10 " mole) DPC under nitrogen and processed as in Example 1.
• the batch reactor is charged with 50 g of polycarbonate oligomer C and 0.404 g (1.223 x 10 "3 mole) MSC under nitrogen and processed as in Example 1.
• Examples 1, 9, 13 polycarbonate oligomers processed without the addition of a branching agent or a combination of a branching agent and a carbonic acid diester.

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