WO2014188359A1 - Procédé de détermination en discontinu de la réactivité intrinsèque de réactifs dans des réactions de polycondensation - Google Patents

Procédé de détermination en discontinu de la réactivité intrinsèque de réactifs dans des réactions de polycondensation Download PDF

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Publication number
WO2014188359A1
WO2014188359A1 PCT/IB2014/061599 IB2014061599W WO2014188359A1 WO 2014188359 A1 WO2014188359 A1 WO 2014188359A1 IB 2014061599 W IB2014061599 W IB 2014061599W WO 2014188359 A1 WO2014188359 A1 WO 2014188359A1
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polycondensation
polycondensation reaction
reaction
reaction mixtures
absorbance spectrum
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PCT/IB2014/061599
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English (en)
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Carlos Godinez Seoane
Jeffrey P. ANNONUEVO
G. Mohammed RAFI
Bander Al-Farhood
Abdulrahman AL-HAZMI
Hatem Abdallah Belfadhel
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Saudi Basic Industries Corporation
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    • 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
    • C08G64/305—General preparatory processes using carbonates and alcohols
    • 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
    • C08G64/205—General preparatory processes characterised by the apparatus used

Definitions

  • the present invention relates methods and systems for determining intrinsic reactivity of polycondensation reactants.
  • the invention relates to a method of determining intrinsic reactivity of polycondensation reactants.
  • the invention relates to a method of determining an intrinsic reactivity using near infrared spectroscopy.
  • the invention relates to a method of determining an intrinsic reactivity using high throughput screening.
  • the present methods of determining intrinsic reactivity enable improved measurement accuracy while reducing the required total analysis time.
  • the invention relates to a method for determining an intrinsic reactivity value of a polycondensation reaction mixture, the method comprising: providing a plurality of at least substantially identical first polycondensation reaction mixtures from a single batch of polycondensation reactants; simultaneously subjecting the plurality of at least substantially identical first polycondensation reaction mixtures to conditions effective to result in a formation of a plurality of second polycondensation reaction mixtures, each comprising at least one polycondensation product; analyzing each of the plurality of second polycondensation reaction mixtures using near infrared spectroscopy to determine an absorbance spectrum of each of the plurality of second polycondensation reaction mixtures; determining a concentration of one or more components present in each of the plurality of second polycondensation reaction mixtures from each absorbance spectrum; and determining an intrinsic reactivity value of the single batch of polycondensation reactants from the determined concentration of the one or more components present in each of the plurality
  • the invention relates to a system for determining an intrinsic reactivity value of a polycondensation reaction mixture, the system comprising: a reaction unit comprising a plurality of reaction vessels; at least one dispensing unit for dispensing a single batch of polycondensation reactants into each of the plurality of reaction vessels such that each reaction vessel contains a substantially identical first polycondensation reaction mixture; a means for simultaneously subjecting each of the first polycondensation reaction mixtures to conditions effective to result in each first
  • polycondensation reaction mixture forming a second polycondensation reaction mixture comprising a polycondensation product; a means for simultaneously subjecting each of the second polycondensation reaction mixtures to conditions effective to result in termination of the reaction; a near infrared spectrometer unit configured to analyze each second
  • polycondensation reaction mixture and to determine an absorbance spectrum of each second polycondensation reaction mixture; and a computing device unit configured to determine an intrinsic reactivity value of the single batch of polycondensation reactants from the determined absorbance spectrum of each second polycondensation reaction mixture.
  • FIG. 1 is a graph representing the influence of the number of replicates on measurement variability.
  • FIG. 2 is a graph representing the quantitative reduction of the confidence interval as a function of the number of replicates.
  • FIG. 3 is a graph representing the spectra and BPA calibration curve for samples measured after being dissolved in dichloromethane.
  • FIG. 4 is a graph representing the spectra and BPA calibration curve for samples measured without solvent intervention.
  • reaction component includes mixtures of two or more reaction components.
  • Ranges can be expressed herein as from one particular value, and/or to another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent 'about,' it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about” that particular value in addition to the value itself. For example, if the value "10" is disclosed, then “about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
  • the terms “about” and “at or about” mean that the amount or value in question can be the value designated some other value approximately or about the same. It is generally understood, as used herein, that it is the nominal value indicated +10% variation unless otherwise indicated or inferred. The term is intended to convey that similar values promote equivalent results or effects recited in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art.
  • an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. It is understood that where "about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.
  • X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.
  • a weight percent (“wt.%”) of a component is based on the total weight of the formulation or composition in which the component is included. For example if a particular element or component in a composition or article is said to have 8% by weight, it is understood that this percentage is relative to a total compositional percentage of 100% by weight.
  • alkyl group is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n propyl, isopropyl, n butyl, isobutyl, t butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like.
  • a "lower alkyl” group is an alkyl group containing from one to six carbon atoms.
  • aryl group as used herein is any carbon-based aromatic group including, but not limited to, benzene, naphthalene, etc.
  • aromatic also includes “heteroaryl group,” which is defined as an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus.
  • the aryl group can be substituted or unsubstituted.
  • the aryl group can be substituted with one or more groups including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy, carboxylic acid, or alkoxy.
  • aralkyl as used herein is an aryl group having an alkyl, alkynyl, or alkenyl group as defined above attached to the aromatic group.
  • An example of an aralkyl group is a benzyl group.
  • carbonate group as used herein is represented by the formula OC(0)OR, where R can be hydrogen, an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above.
  • number average molecular weight or “M n” can be used interchangeably, and refer to the statistical average molecular weight of all the polymer chains in the sample and is defined by the formula:
  • M n can be determined for polymers, e.g. polycarbonate polymers, by methods well known to a person having ordinary skill in the art using molecular weight standards, e.g. polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards.
  • weight average molecular weight or “Mw” can be used interchangeably, and are defined by the formula:
  • Mj is the molecular weight of a chain and Nj is the number of chains of that molecular weight.
  • M w takes into account the molecular weight of a given chain in determining contributions to the molecular weight average.
  • M w can be determined for polymers, e.g. polycarbonate polymers, by methods well known to a person having ordinary skill in the art using molecular weight standards, e.g. polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards.
  • polycarbonate refers to an oligomer or polymer comprising residues of one or more dihydroxy compounds, e.g. dihydroxy aromatic compounds, joined by carbonate linkages; it also encompasses homopolycarbonates, copolycarbonates, and (co)polyester carbonates.
  • constituents of the polymers are synonymous throughout the specification.
  • condition effective to refers to such amount or condition that is capable of performing the function or property for which an effective amount is expressed. As will be pointed out below, the exact amount or particular condition required will vary from one aspect to another, depending on recognized variables such as the materials employed and the processing conditions observed. Thus, it is not always possible to specify an exact “effective amount” or “condition effective to.” However, it should be understood that an appropriate effective amount will be readily determined by one of ordinary skill in the art using only routine experimentation .
  • compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.
  • the present invention relates to a method for determining intrinsic reactivity of a component in a polycondensation reaction mixture.
  • the invention relates to a method of determining an intrinsic reactivity using near infrared spectroscopy.
  • the invention relates to a method of determining an intrinsic reactivity using a high number of replicates.
  • the present methods of determining intrinsic reactivity enable improved measurement accuracy while reducing the required total analysis time.
  • determining an intrinsic reactivity value of a polycondensation reaction mixture comprising: providing a plurality of at least substantially identical first polycondensation reaction mixtures from a single batch of polycondensation reactants; simultaneously subjecting the plurality of at least substantially identical first polycondensation reaction mixtures to conditions effective to result in a formation of a plurality of second polycondensation reaction mixtures, each comprising at least one polycondensation product; analyzing each of the plurality of second polycondensation reaction mixtures using near infrared spectroscopy to determine an absorbance spectrum of each of the plurality of second polycondensation reaction mixtures; determining a concentration of one or more components present in each of the plurality of second polycondensation reaction mixtures from each absorbance spectrum; and determining an intrinsic reactivity value of the single batch of polycondensation reactants from the determined concentration of the one or more components present in each of the plurality of second poly
  • the present invention pertains to polycondensation reaction mixtures.
  • the polycondensation reaction mixtures comprise a first polycondensation reaction mixture, second polycondensation reaction mixture,
  • polycondensation reactant or polycondensation product, or combinations thereof.
  • the polycondensation reaction mixtures comprise at least one reaction component.
  • the reaction component comprises starting reactants, chemical intermediates, reaction by-products, or end products, or combinations thereof.
  • the starting reactants can comprise bisphenol A (BPA) or diphenyl carbonate (DPC)
  • the chemical intermediates can comprise oligomers
  • the reaction by-products can comprise phenol
  • the end products can comprise a final polymer.
  • the reaction component can be present in any concentration.
  • the reaction component can be present in an amount in the range of from single molecules up to about 100 weight % relative to the total weight of the polycondensation reaction mixture, including further exemplary amounts of about 5 weight %, about 10 weight %, 15 weight %, 20 weight %, 25 weight%, 30 weight %, 35 weight %, 40 weight %, 45 weight %, 50 weight %, 55 weight %, 60 weight %, 65 weight %, 70 weight %, 75 weight %, 80 weight %, 85 weight %, 90 weight %, about 95 weight %.
  • the reaction component can be present within any range of amount derived from any two of the above stated values.
  • the reaction component can be present in an amount in the range of from about 5 to about 15 weight %, or in an amount in the range of from about 5 weight % to about 20 weight %, or in an amount in the range of from about 50 weight % to about 85 weight % relative to the total weight of the polycondensation reaction mixture.
  • the polycondensation reaction mixtures comprise individual samples.
  • the polycondensation reaction mixtures comprise a plurality of individual polycondensation reaction mixtures.
  • the plurality of polycondensation reaction mixtures comprise an array.
  • the array can comprise a first-order array, a second-order array, or a multi-order array, or combinations thereof.
  • the array may be arranged in a spatially defined array, for example, in a multi-well microtiter plate.
  • the multi-well microtiter plate can comprise any number of wells, including, but not limited to 96- well, 192-well, 384- well microtiter plates.
  • each of the plurality of polycondensation reaction mixtures can comprise substantially identical polycondensation reaction mixtures. In a still further aspect, each of the plurality of polycondensation reaction mixtures can comprise different polycondensation reaction mixtures. In a yet further aspect, the plurality of polycondensation reaction mixtures can comprise individual samples, multiple individual samples arranged in a fixed configuration, or a plurality of individual samples.
  • the polycondensation reaction mixtures are formed from polycondensation reactants.
  • polycondensation reaction mixtures are formed from a single batch of polycondensation reactants.
  • first polycondensation reaction mixtures are formed from a single batch of polycondensation reactants, for example, new polycondensation reactants that have not been previously tested or used.
  • polycondensation reactants are reacted in the presence of a catalyst, high temperature and vacuum conditions in order to achieve a high molecular weight product.
  • catalysts of a basic nature are involved in very low concentrations (parts per billion range) with respect to the limiting reagent.
  • polycondensation reactants can comprise impurities, and the presence in the polycondensation reactants of minute impurities in concentrations of the same order of magnitude can partially or completely deactivate the catalyst.
  • the level or amount of impurities is unknown, and impurity influence on deactivation kinetics can be difficult to predict.
  • the methods comprise second polycondensation reaction mixtures.
  • the second polycondensation reaction mixtures are formed from first polycondensation reaction mixtures.
  • the polycondensation reaction mixtures comprise at least one polycondensation product.
  • the polycondensation reaction mixture comprises a polycarbonate reaction mixture.
  • the polycarbonate reaction mixture comprises a polycarbonate melt polymerization mixture.
  • the polycondensation product comprises a polycarbonate, a polycarbonate product, or an intermediate polycarbonate product, or combinations thereof.
  • a polycarbonate can comprise any polycarbonate material or mixture of materials, for example, as recited in U.S. Patent No. 7,786,246, which is hereby incorporated in its entirety for the specific purpose of disclosing various polycarbonate compositions and methods.
  • the term polycarbonate can be further defined as compositions have repeating structural units of the formula (1):
  • each R 1 is an aromatic organic radical and, more preferably, a radical of the formula (2):
  • radicals of this type include, but are not limited to, radicals such as -0-, -S-, -S(O) -, -S(0 2 ) -, -C(O) -, methylene, cyclohexyl-methylene, 2-[2.2.1]- bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene,
  • the bridging radical Y 1 is preferably a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene, or isopropylidene.
  • polycarbonates can be produced by the reaction of dihydroxy compounds having the formula HO— R 1 — OH, which includes dihydroxy compounds of formula (3): HO- A -Y -A ⁇ OH (3),
  • R and R b each represent a halogen atom or a monovalent hydrocarbon group and can be the same or different; p and q are each independently integers from 0 to 4; and X represents one of the groups of formula (5):
  • R c and R d each independently represent a hydrogen atom or a monovalent linear or cyclic hydrocarbon group and R e is a divalent hydrocarbon group.
  • suitable dihydroxy compounds include the dihydroxy-substituted hydrocarbons disclosed by name or formula (generic or specific) in U.S. Pat. No. 4,217,438.
  • a nonexclusive list of specific examples of suitable dihydroxy compounds includes the following: resorcinol, 4-bromoresorcinol, hydroquinone, 4,4'- dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4- hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)- 1- naphthylmethane, 1 ,2-bis(4-hydroxyphenyl)ethane, 1 , 1 -bis(4-hydroxyphenyl)- 1 -phenylethane, 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenyl
  • examples of the types of bisphenol compounds that can be represented by formula (3) includes l,l-bis(4-hydroxyphenyl)methane, l,l-bis(4- hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (hereinafter "bisphenol A” or "BPA”), 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, l,l-bis(4- hydroxyphenyl)propane, l,l-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-l- methylphenyl)propane, and l,l-bis(4-hydroxy-t-butylphenyl)propane.
  • BPA 2,2-bis(4-hydroxyphenyl)propane
  • BPA 2,2-bis(4-hydroxyphenyl)butane
  • BPA 2,2-bis(4-hydroxyphenyl)octan
  • a polycarbonate can employ two or more different dihydroxy compounds or a copolymer of a dihydroxy compounds with a glycol or with a hydroxy- or acid-terminated polyester or with a dibasic acid or hydroxy acid in the event a carbonate copolymer rather than a homopolymer is desired for use.
  • Polyarylates and polyester-carbonate resins or their blends can also be employed.
  • Branched polycarbonates are also useful, as well as blends of linear polycarbonate and a branched polycarbonate. The branched polycarbonates can be prepared by adding a branching agent during polymerization.
  • the branching agents include polyfunctional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures thereof.
  • Specific examples include trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-p-hydroxy phenyl ethane, isatin-bis- phenol, tris-phenol TC (l,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA (4(4(1, l-bis(p-hydroxyphenyl)-ethyl)alpha, alpha-dimethyl benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid.
  • the branching agents can be added at a level of from 0.05-2.0 weight percent.
  • Branching agents and procedures for making branched polycarbonates are described in U.S. Pat. Nos. 3,635,895 and 4,001,184. All types of polycarbonate end groups are contemplated as being useful in the thermoplastic composition.
  • the polycarbonates are based on bisphenol A, in which each of A 1 and A2 is p-phenylene and Y 1 is isopropylidene.
  • the molecular weight (Mw) of the polycarbonate is about 10,000 to about 100,000.
  • the polycarbonate has a Mw of about 15,000 to about 55,000.
  • the polycarbonate has a Mw of about 18,000 to about 40,000.
  • Polycarbonates including isosorbide-based polyester-polycarbonate, can comprise copolymers comprising carbonate units and other types of polymer units, including ester units, and combinations comprising at least one of homopolycarbonates and
  • copolycarbonates An exemplary polycarbonate copolymer of this type is a polyester carbonate, also known as a polyester-polycarbonate. Such copolymers further contain carbonate units derived from oligomeric ester-containing dihydroxy compounds (also referred to herein as hydroxy end-capped oligomeric acrylate esters).
  • the polycondensation reaction mixtures are subject to conditions effective to result in a formation of polycondensation reaction mixtures comprising a polycondensation product.
  • the first polycondensation reaction mixtures are subject to conditions effective to result in a formation of second polycondensation reaction mixtures.
  • the polycondensation reaction mixtures are subjected to conditions effective to terminate the reaction.
  • polycondensation reaction mixtures are simultaneously subjected to conditions effective to terminate the reaction.
  • the resulting polycondensation reaction mixture can comprise unreacted starting reactants, chemical intermediates, reaction by-products, or end products, or combinations thereof.
  • the polycondensation reaction mixtures are subjected to conditions effective to result in formation of at least one polycarbonate polycondensation product.
  • conditions effective comprise reaction conditions of a melt polymerization reaction, for example, reaction conditions and components involved in the melt polymerization of polycarbonates.
  • polycarbonates are prepared by co-reacting, in a molten state, the dihydroxy reactant(s) (i.e., isosorbide, aliphatic diol and/or aliphatic diacid, and any additional dihydroxy compound) and a diaryl carbonate ester, such as diphenyl carbonate, or more specifically in an aspect, an activated carbonate such as bis(methyl salicyl)carbonate, in the presence of a dihydroxy reactant(s) (i.e., isosorbide, aliphatic diol and/or aliphatic diacid, and any additional dihydroxy compound) and a diaryl carbonate ester, such as diphenyl carbonate, or more specifically in an aspect, an activated carbonate such as bis(methyl salicyl)carbonate, in the presence of a
  • transesterification catalyst The reaction can be carried out in typical polymerization equipment, such as one or more continuously stirred reactors (CSTRs), plug flow reactors, wire wetting fall polymerizers, free fall polymerizers, wiped film polymerizers, BANBURY® mixers, single or twin screw extruders, or combinations of the foregoing.
  • CSTRs continuously stirred reactors
  • plug flow reactors plug flow reactors
  • wire wetting fall polymerizers free fall polymerizers
  • free fall polymerizers wiped film polymerizers
  • BANBURY® mixers single or twin screw extruders, or combinations of the foregoing.
  • volatile monohydric phenol can be removed from the molten reactants by distillation and the polymer is isolated as a molten residue.
  • the melt polymerization can include a transesterification catalyst comprising a first catalyst, also referred to herein as an alpha catalyst, comprising a metal cation and an anion.
  • a transesterification catalyst comprising a first catalyst, also referred to herein as an alpha catalyst, comprising a metal cation and an anion.
  • the cation is an alkali or alkaline earth metal comprising Li, Na, K, Cs, Rb, Mg, Ca, Ba, Sr, or a combination comprising at least one of the foregoing.
  • the anion is hydroxide (OH “ ), superoxide (O 2 " ), thiolate (HS “ ), sulfide (S 2 " ), a C 1-2 o alkoxide, a C 6 -2o aryloxide, a C 1-2 o carboxylate, a phosphate including biphosphate, a C 1-2 o phosphonate, a sulfate including bisulfate, sulfites including bisulfites and metabisulfites, a Ci-20 sulfonate, a carbonate including bicarbonate, or a combination comprising at least one of the foregoing.
  • salts of an organic acid comprising both alkaline earth metal ions and alkali metal ions can also be used.
  • Salts of organic acids useful as catalysts are illustrated by alkali metal and alkaline earth metal salts of formic acid, acetic acid, stearic acid and ethyelenediaminetetraacetic acid.
  • the catalyst can also comprise the salt of a nonvolatile inorganic acid.
  • nonvolatile it is meant that the referenced compounds have no appreciable vapor pressure at ambient temperature and pressure. In particular, these compounds are not volatile at temperatures at which melt polymerizations of polycarbonate are typically conducted.
  • the salts of nonvolatile acids are alkali metal salts of phosphites; alkaline earth metal salts of phosphites; alkali metal salts of phosphates; and alkaline earth metal salts of phosphates.
  • Exemplary transesterification catalysts include, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium formate, sodium formate, potassium formate, cesium formate, lithium acetate, sodium acetate, potassium acetate, lithium carbonate, sodium carbonate, potassium carbonate, lithium methoxide, sodium methoxide, potassium
  • the transesterification catalyst is an alpha catalyst comprising an alkali or alkaline earth salt.
  • the transesterification catalyst comprises sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, NaH 2 P0 4 , or a combination comprising at least one of the foregoing.
  • the amount of alpha catalyst can vary widely according to the conditions of the melt polymerization, and can be about 0.001 to about 500 micromoles ( ⁇ ). In an aspect, the amount of alpha catalyst can be about 0.01 to about 20 ⁇ , specifically about 0.1 to about 10 ⁇ , more specifically about 0.5 to about 9 ⁇ , and still more specifically about 1 to about 7 ⁇ , per mole of aliphatic diol and any other dihydroxy compound present in the melt polymerization.
  • a second transesterification catalyst also referred to herein as a beta catalyst
  • a second transesterification catalyst can optionally be included in the melt polymerization process, provided that the inclusion of such a second transesterification catalyst does not significantly adversely affect the desirable properties of the polycarbonate.
  • exemplary transesterification catalysts can further include a combination of a phase transfer catalyst of formula (R 3 ) 4 Q + X above, wherein each R is the same or different, and is a Ci.io alkyl group; Q is a nitrogen or phosphorus atom; and X is a halogen atom or a C 1-8 alkoxy group or C 6 -is aryloxy group.
  • Exemplary phase transfer catalyst salts include, for example, [CH 3 (CH 2 )3] 4 NX,
  • tetrabutylammonium hydroxide methyltributylammonium hydroxide, tetrabutylammonium acetate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate,
  • melt transesterification catalysts include alkaline earth metal salts or alkali metal salts.
  • the beta catalyst can be present in a molar ratio, relative to the alpha catalyst, of less than or equal to 10, specifically less than or equal to 5, more specifically less than or equal to 1, and still more specifically less than or equal to 0.5.
  • the melt polymerization reaction disclosed herein uses only an alpha catalyst as described hereinabove, and is substantially free of any beta catalyst. As defined herein, "substantially free of can mean where the beta catalyst has been excluded from the melt polymerization reaction.
  • the beta catalyst is present in an amount of less than about 10 parts per million (ppm), specifically less than 1 ppm, more specifically less than about 0.1 ppm, more specifically less than or equal to about 0.01 ppm, and more specifically less than or equal to about 0.001 ppm, based on the total weight of all components used in the melt polymerization reaction.
  • ppm parts per million
  • an end-capping agent (also referred to as a chain-stopper) can optionally be used to limit molecular weight growth rate, and so control molecular weight in the polycarbonate.
  • exemplary chain-stoppers include certain monophenolic compounds (i.e., phenyl compounds having a single free hydroxy group), monocarboxylic acid chlorides, and/or monochloroformates.
  • Phenolic chain- stoppers are exemplified by phenol and C1-C22 alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p- and tertiary-butyl phenol, cresol, and monoethers of diphenols, such as p-methoxyphenol.
  • Alkyl- substituted phenols with branched chain alkyl substituents having 8 to 9 carbon atoms can be specifically mentioned.
  • endgroups can be derived from the carbonyl source (i.e., the diaryl carbonate), from selection of monomer ratios, incomplete polymerization, chain scission, and the like, as well as any added end-capping groups, and can include derivatizable functional groups such as hydroxy groups, carboxylic acid groups, or the like.
  • the endgroup of a polycarbonate, including a polycarbonate polymer as defined herein can comprise a structural unit derived from a diaryl carbonate, where the structural unit can be an endgroup.
  • the endgroup is derived from an activated carbonate.
  • Such endgroups can be derived from the transesterification reaction of the alkyl ester of an appropriately substituted activated carbonate, with a hydroxy group at the end of a polycarbonate polymer chain, under conditions in which the hydroxy group reacts with the ester carbonyl from the activated carbonate, instead of with the carbonate carbonyl of the activated carbonate.
  • structural units derived from ester containing compounds or substructures derived from the activated carbonate and present in the melt polymerization reaction can form ester endgroups.
  • the melt polymerization reaction can be conducted by subjecting the polycondensation reaction mixtures to a series of temperature-pressure-time protocols. In some aspects, this involves gradually raising the reaction temperature in stages while gradually lowering the pressure in stages. In one aspect, the pressure is reduced from about atmospheric pressure at the start of the reaction to about 1 millibar (100 Pascals (Pa)) or lower, or in another aspect to 0.1 millibar (10 Pa) or lower in several steps as the reaction approaches completion.
  • the temperature can be varied in a stepwise fashion beginning at a temperature of about the melting temperature of the polycondensation reaction mixture and subsequently increased to final temperature. In one aspect, the polycondensation reaction mixture is heated from room temperature to about 150 ° C. In such an aspect, the
  • polymerization reaction starts at a temperature of about 150 ° C to about 220 ° C.
  • the polymerization temperature can be up to about 220 ° C.
  • the polymerization reaction can then be increased to about 250 ° C and then optionally further increased to a temperature of about 320 ° C, and all subranges there between.
  • the total reaction time can be from about 30 minutes to about 360 minutes and all subranges there between. This procedure will generally ensure that the reactants react to give polycarbonates with the desired molecular weight, glass transition temperature and physical properties.
  • the reaction proceeds to build the polycarbonate chain with production of ester-substituted alcohol by-product such as methyl salicylate.
  • efficient removal of the by-product can be achieved by different techniques such as reducing the pressure. Generally the pressure starts relatively high in the beginning of the reaction and is lowered progressively throughout the reaction and temperature is raised throughout the reaction. After the desired melt viscosity and/or molecular weight is reached, the final polycarbonate product can be isolated from the reactor in a solid or molten form.
  • the disclosed methods comprise analyzing a plurality of polycondensation reaction mixtures or reaction components.
  • each of the plurality of individual polycondensation reaction mixtures is analyzed substantially simultaneously.
  • each of the plurality of individual polycondensation reaction mixtures is analyzed separately.
  • the disclosed methods comprise analyzing the
  • NIR near-infrared spectroscopy
  • NIR near-infrared spectroscopy
  • near-infrared spectroscopy is an analytical method that uses the near-infrared region of the electromagnetic spectrum (from about 800 nanometers (nm) to 2500 nm) for qualitative or quantitative chemical analysis.
  • the NIR molecular overtones and combined absorption bands are typically very broad, leading to complex spectra and making difficult to assign specific features to specific chemical components.
  • the measured absorbance spectrum comprises at least one wavelength in the range from about 800 nm to 2500 nm. In a still further aspect, the measured absorbance spectrum comprises at least one wavelength in the range from about 1500 nm to 2000 nm. In a yet further aspect, the absorbance spectrum comprises multiple wavelengths. In an even further aspect, the absorbance spectrum comprises at least one entire absorption band.
  • the disclosed methods comprise application of
  • one wavelength is used to determine a concentration of one or more reaction components.
  • concentrations of reaction components are determined using mathematical analysis techniques comprising univariate analysis.
  • multiple wavelengths are used to determine a concentration of one or more reaction components.
  • reaction component concentrations are determined using mathematical analysis techniques comprising multivariate analysis.
  • multivariate analysis comprises principal components analysis, partial least squares analysis, artificial neural networks analysis, linear multivariate analysis, or nonlinear multivariate analysis.
  • concentration of reaction components are performed using computer software.
  • the computer software can comprise any computer software suitable for use in performing calculations employed in determining concentrations of reaction components.
  • Non-limiting examples of computer software include MATLAB, TQ Analyst Quantification Software, and MINITAB.
  • analyzing comprises irradiating each of the plurality of individual polycondensation reaction mixtures with at least one wavelength of near infrared radiation and measuring the absorbance spectrum of each of the plurality of individual polycondensation reaction mixtures, and correlating absorbance values to concentrations of a reaction component.
  • the disclosed methods comprise determining an intrinsic reactivity of polycondensation reactants.
  • the polycondensation reactions comprise a single batch of polycondensation reactants.
  • the intrinsic reactivity is determined using the calculated concentration of the one or more components present in a polycondensation reaction mixture, for example, using the concentration of one or more components present in each of the plurality of the second polycondensation reaction mixtures.
  • the intrinsic reactivity is determined by comparing the degree of conversion exhibited by a polycondensation reactant with the degree of conversion of a known reference sample tested in substantially the same reaction conditions.
  • the intrinsic reactivity is used to determine deactivation kinetics of previously untested polycondensation reactants.
  • the intrinsic reactivity permits determination of the effect on reactivity from impurities formed from the untested polycondensation reactants during the polycondensation reaction.
  • the intrinsic reactivity values can thus be used to determine the correction factor needed to overcome impurity influence on deactivation kinetics.
  • the correction factor can comprise adjustment in the amount of catalyst added to the polycondensation reaction mixtures.
  • the present invention also relates to a system for determining an intrinsic reactivity value of a polycondensation reaction mixture, the system comprising: a reaction unit comprising a plurality of reaction vessels; at least one dispensing unit for dispensing a single batch of polycondensation reactants into each of the plurality of reaction vessels such that each reaction vessel contains a substantially identical first polycondensation reaction mixture; a means for simultaneously subjecting each of the first polycondensation reaction mixtures to conditions effective to result in each first
  • polycondensation reaction mixture forming a second polycondensation reaction mixture comprising a polycondensation product; a means for simultaneously subjecting each of the second polycondensation reaction mixtures to conditions effective to result in termination of the reaction; a near infrared spectrometer unit configured to analyze each second
  • polycondensation reaction mixture and to determine an absorbance spectrum of each second polycondensation reaction mixture; and a computing device unit configured to determine an intrinsic reactivity value of the single batch of polycondensation reactants from the determined absorbance spectrum of each second polycondensation reaction mixture.
  • the reaction unit comprises individual reaction vessels.
  • the reaction unit comprises a plurality of individual reaction vessels.
  • the reaction vessels comprise glass or quartz vials.
  • the reaction unit comprises an array.
  • the array can comprise a first-order array, a second-order array, or a multi-order array, or combinations thereof.
  • the array may be arranged in a spatially defined array, for example, in a multi-well or multi-vessel microtiter plate.
  • the microtiter plate can comprise any number of wells or vessels, including, but not limited to 96-well, 192- well, 384-well microtiter plates.
  • each of the plurality of polycondensation reaction mixtures is dispensed in and reside in an individual reaction vessel.
  • the system comprises at least one dispensing unit for metering, dosing, and dispensing of the polycondensation reactants.
  • the dispensing unit comprises a gravimetric dispensing system or a volumetric dispensing system.
  • the polycondensation reactants are dispensed in the reaction vessels simultaneously or successively.
  • the system comprises a means for controlling the reaction conditions of the reaction unit, for example, by controlling temperature or pressure.
  • the system comprises a means for subjecting polycondensation reaction mixtures to conditions effective to result in a formation of polycondensation reaction mixtures comprising a polycondensation product, for example, a means for controlling temperature or pressure.
  • the first polycondensation reaction mixtures are subject to conditions effective to result in a formation of second polycondensation reaction mixtures.
  • system comprises a means for subjecting
  • conditions effective to terminate the reaction comprise fast cooling the mixture, for example, to a temperature below which kinetics are inhibited.
  • conditions effective to terminate the reaction comprise adding a chemical capable of neutralizing the catalyst.
  • conditions effective to terminate the reaction comprises adding a chemical capable of reacting with a chain ends to produce a new chain which is chemically incapable of further growth.
  • all the polycondensation reaction mixtures are simultaneously subjected to same reaction conditions. In a yet further aspect, all the polycondensation reaction mixtures are simultaneously subjected to conditions effective to terminate the reaction. Depending on the total reaction time, the resulting polycondensation reaction mixture can comprise unreacted starting reactants, chemical intermediates, reaction by-products, or end products, or combinations thereof.
  • the means for controlling temperature or pressure comprise a temperature control unit or a pressure control unit, respectively.
  • the temperature control unit comprises a heating unit, or a cooling unit, or a combination thereof.
  • the means for subjecting the polycondensation reaction mixtures to conditions effective results in formation of at least one polycarbonate
  • conditions effective comprise reaction conditions of a melt polymerization reaction, for example, reaction conditions and components involved in the melt polymerization of polycarbonates.
  • the means for subjecting to conditions effective comprises an admixing unit.
  • the admixing unit shakes or agitates the reaction unit or reaction vessels to cause mixing of the polycondensation reactants and formation of a polycondensation reaction mixture.
  • the admixing unit comprises a means for stirring the plurality of polycondensation reaction mixtures.
  • the means for stirring comprises a plurality of stirring instruments.
  • each of the plurality of stirring instruments corresponds to a reaction vessel.
  • the means for subjecting to conditions effective comprise a temperature control unit.
  • the temperature control unit comprises a heating unit, or a cooling unit, or a combination thereof.
  • the heating unit comprises a heating element.
  • suitable heating element include heat plates, heat lamps, and heating baths using suitable heat transfer media, for example, using hot water, hot oil, or fluidized sand.
  • the cooling unit comprises a cooling element.
  • the cooling element can comprise any cooling element suitable for use in terminating a reaction.
  • Non- limiting examples of cooling elements include refrigerated baths using cooling transfer media, for example, using chilled water, brine, Freon, ammonia or sublimating solid carbon dioxide.
  • the system comprises a near infrared spectrometer unit configured to analyze the polycondensation reaction mixtures.
  • the near infrared spectrometer unit is configured to analyze a single reaction vessel.
  • the near infrared spectrometer unit is configured to analyze a plurality of reaction vessels.
  • the NIR spectrometer unit is configured to analyze the plurality of reaction vessels simultaneously or in parallel.
  • the system comprises a Raman spectrometer unit configured to analyze the polycondensation reaction mixtures.
  • the system comprises a UV-Vis spectrometer unit configured to analyze the polycondensation reaction mixtures.
  • the NIR unit is configured to determine absorbance spectrum or spectroscopic data which are evaluated as described herein.
  • the absorbance spectrum measured by the NIR spectrometer unit comprises at least one wavelength in the range of from 800 nm to 2500 nm.
  • the absorbance spectrum comprises at least one wavelength in the range of from 1500 nm to 2000 nm.
  • the absorbance spectrum comprises multiple wavelengths. In still further aspects, the absorbance spectrum comprises an entire absorption band.
  • the NIR spectrometer unit is configured to irradiate each of the plurality of individual polycondensation reaction mixtures with at least one wavelength of near infrared radiation and configured to determine the absorbance spectrum of each of the plurality of individual polycondensation reaction mixtures.
  • the system comprises a computing device unit configured to receive the determined absorbance spectrum data from the NIR spectroscopic unit.
  • the computing device unit is configured to perform mathematical analysis of the determined absorbance spectrum to extract chemical information.
  • the chemical information comprises the concentration of at least one reaction component present in a polycondensation reaction mixture.
  • the mathematical analysis comprises determining the concentration of at least one reaction component using the determined absorbance spectrum.
  • the computing device unit comprises computing hardware and software for performing mathematical analysis of the absorbance spectrum to extract chemical information.
  • the software performs one or more steps relating to application of mathematical analysis techniques to extract chemical information.
  • the software can comprise any computer software suitable for use in performing calculations employed in determining concentrations of reaction components.
  • Non-limiting examples of computer software include MATLAB, TQ Analyst Quantification Software, and MINITAB.
  • the computing device unit uses one wavelength of the absorbance spectrum to determine a concentration of at least one reaction component. In further aspects, determining the concentration of at least one reaction component using one wavelength comprises univariate analysis.
  • the computing device unit uses multiple wavelengths to determine the concentration of at least one reaction component.
  • determining the concentration of at least one reaction components comprises multivariate analysis.
  • multivariate analysis comprises neural networks analysis, principal components analysis, partial least squares analysis, linear multivariate analysis, or nonlinear multivariate analysis.
  • the computing device unit determines an intrinsic reactivity value by comparing the degree of conversion exhibited by a polycondensation reactant with the degree of conversion of a known reference sample tested in substantially the same reaction conditions.
  • system parts or steps can be manual or automated.
  • at least a portion of system parts or steps are electrically driven.
  • at least a portion of the system parts or steps are performed by a robotic device.
  • the present methods and system provide advantages over standard reactivity tests of the prior art.
  • one drawback of standard reactivity tests is their accuracy.
  • standard reactivity tests lack the requisite repeatability and reproducibility needed to make it a useful aspect in control strategies of polycondensation reactions.
  • Another drawback to standard reactivity test is its high duration of reaction, which in various aspects, diminishes any value it has in taking corrective actions in a polycondensation plant environment.
  • the disclosed methods and systems provide improved measurement accuracy while reducing the total analysis time.
  • the disclosed methods and systems exhibit a Gage Repeatability and Reproducibility (GRR) of less than or equal to 30%.
  • Gage Repeatability and Reproducibility (GRR) is less than or equal to 25%.
  • the disclosed methods and systems exhibit improved influence on confidence intervals.
  • the number of replicates the disclosed methods and systems exhibit improved influence on confidence intervals.
  • polycondensation reaction mixtures analyzed is sufficient to produce a predicted confidence interval of at least about 95%. In a further aspect, the number of polycondensation reaction mixtures analyzed is sufficient to produce a predicted confidence interval of at least about 98%.
  • the present invention pertains to and includes at least the following aspects.
  • a method for determining an intrinsic reactivity value of a polycondensation reaction mixture comprising: a) providing a plurality of at least substantially identical first polycondensation reaction mixtures from a single batch of polycondensation reactants; b) simultaneously subjecting the plurality of at least substantially identical first polycondensation reaction mixtures to conditions effective to result in a formation of a plurality of second polycondensation reaction mixtures, each comprising at least one polycondensation product; c) analyzing each of the plurality of second
  • polycondensation reaction mixtures using near infrared spectroscopy to determine an absorbance spectrum of each of the plurality of second polycondensation reaction mixtures; d) determining a concentration of one or more components present in each of the plurality of second polycondensation reaction mixtures from each absorbance spectrum; and e) determining an intrinsic reactivity value of the single batch of polycondensation reactants from the determined concentration of the one or more components present in each of the plurality of second polycondensation reaction mixtures.
  • Aspect 2 The method of aspect 1, wherein the polycondensation reaction mixture comprises a polycarbonate polymerization reaction mixture.
  • Aspect 3 The method of any preceding aspect, wherein the reaction component comprises starting reactants, chemical intermediates, reaction by-products, or end products, or combinations thereof.
  • Aspect 4 The method according to any preceding aspect, wherein the reaction component comprises bisphenol A, diphenyl carbonate, an oligomer, phenol, or a polycarbonate polymer, or combinations thereof.
  • Aspect 5 The method according to any preceding aspect, wherein the reaction component is present in an amount from greater than 0 weight% to 100 weight % of polycondensation reaction mixture.
  • Aspect 6 The method according to any preceding aspect, wherein the reaction component comprises DPC.
  • reaction component comprises BPA.
  • Aspect 8 The method according to any preceding aspect, wherein the reaction component comprises phenol.
  • Aspect 9 The method according to any preceding aspect, wherein the polycondensation reactants comprise an aromatic dihydroxy compound or a diaryl carbonate ester.
  • Aspect 10 The method according to any preceding aspect, wherein the polycondensation reactants comprise bisphenol A (BPA) or diphenyl carbonate (DPC).
  • BPA bisphenol A
  • DPC diphenyl carbonate
  • Aspect 11 The method according to any preceding aspect, wherein conditions effective comprise reaction conditions of a melt polymerization reaction.
  • Aspect 12 The method according to any preceding aspect, wherein the plurality of reaction mixtures comprises an array.
  • Aspect 13 The method according to any preceding aspect, wherein the plurality of reaction mixtures comprises a first-order array.
  • Aspect 14 The method according to any preceding aspect, wherein the plurality of reaction mixtures comprises a second-order or higher array.
  • Aspect 15 The method according to any preceding aspect, wherein the plurality of reaction mixtures comprises a multi-order array.
  • Aspect 16 The method according to any preceding aspect, wherein the plurality of reaction mixtures comprise a multi-well microtiter plate.
  • Aspect 17 The method according to any preceding aspect, wherein the plurality of reaction mixtures comprise individual samples, multiple individual samples arranged in a fixed configuration, or a plurality of individual samples.
  • Aspect 18 The method according to any preceding aspect, wherein analyzing each of the plurality of individual polycondensation reaction mixtures is substantially simultaneous.
  • Aspect 19 The method according to any preceding aspect, wherein analyzing each of the plurality of individual polycondensation reaction mixtures is separate.
  • Aspect 20 The method according to any preceding aspect, further comprising simultaneously subjecting the plurality of the second polycondensation reaction mixtures to conditions effective to terminate the reaction.
  • Aspect 21 The method according to any preceding aspect, wherein the polycondensation product comprises a polycarbonate product or intermediate polycarbonate product.
  • Aspect 22 The method according to any preceding aspect, wherein analyzing comprises irradiating each of the plurality of individual polycondensation reaction mixtures with at least one wavelength of near infrared radiation and measuring the absorbance spectrum of each of the plurality of individual polycondensation reaction mixtures, and correlating absorbance values to levels of a reaction component.
  • Aspect 23 The method according to any preceding aspect, wherein absorbance spectrum comprises at least one wavelength in the range of from 800 nm to 2500 nm.
  • Aspect 24 The method according to any preceding aspect, wherein absorbance spectrum comprises at least one wavelength in the range of from 1500 nm to 2000 nm.
  • Aspect 25 The method according to any preceding aspect, wherein absorbance spectrum comprises multiple wavelengths.
  • Aspect 26 The method according to any preceding aspect, wherein absorbance spectrum comprises an entire absorption band.
  • Aspect 27 The method according to any preceding aspect, wherein one wavelength is used to determine a concentration of one or more reaction components.
  • Aspect 28 The method according to any preceding aspect, wherein determining a concentration of one or more reaction components comprises univariate analysis.
  • Aspect 29 The method according to any preceding aspect, wherein multiple wavelengths are used to determine a concentration of one or more reaction components.
  • Aspect 30 The method according to any preceding aspect, wherein determining a concentration of one or more reaction components comprises multivariate analysis.
  • Aspect 31 The method according to any preceding aspect, wherein multivariate analysis comprises neural networks analysis, principal components analysis, partial least squares analysis, linear multivariate analysis, or nonlinear multivariate analysis.
  • Aspect 32 The method according to any preceding aspect, wherein at least one step in determining a concentration of one or more reaction components is performed using computer software.
  • Aspect 33 The method according to any preceding aspect, wherein determining an intrinsic reactivity comprises comparing the degree of conversion exhibited by a polycondensation reactant with the degree of conversion of a known reference sample tested in substantially the same reaction conditions.
  • Aspect 34 The method according to any preceding aspect, wherein the intrinsic reactivity is used to determine deactivation kinetics of the polycondensation reaction mixture.
  • Aspect 35 The method according to any preceding aspect, wherein the Gage repeatability and reproducibility (GRR) is less than or equal to 30%.
  • GRR Gage repeatability and reproducibility
  • Aspect 36 The method according to any preceding aspect, wherein the Gage repeatability and reproducibility (GRR) is less than or equal to 25%.
  • GRR Gage repeatability and reproducibility
  • Aspect 37 The method according to any preceding aspect, wherein the number of polycondensation reaction mixtures analyzed is sufficient to produce a predicted confidence interval of at least about 95%.
  • Aspect 38 The method according to any preceding aspect, wherein the number of polycondensation reaction mixtures analyzed is sufficient to produce a predicted confidence interval of at least about 98%.
  • a method for determining an intrinsic reactivity value of a polycondensation reaction mixture comprising: a) providing a plurality of at least substantially identical first polycondensation reaction mixtures from a single batch of polycondensation reactants; b) simultaneously subjecting the plurality of at least substantially identical first polycondensation reaction mixtures to conditions effective to result in a formation of a plurality of second polycondensation reaction mixtures, each comprising at least one polycondensation product; c) simultaneously subjecting the plurality of the second polycondensation reaction mixtures to conditions effective to terminate the reaction; d) analyzing each of the plurality of second polycondensation reaction mixtures using near infrared spectroscopy to determine an absorbance spectrum of each of the plurality of second polycondensation reaction mixtures; e)determining a concentration of one or more components present in each of the plurality of second polycondensation reaction mixtures from each absorbance spectrum; and f)determining an intrinsic
  • a method for determining an intrinsic reactivity value of a polycondensation reaction mixture comprising: a) providing a plurality of at least substantially identical first polycondensation reaction mixtures from a single batch of polycondensation reactants comprising bisphenol A (BPA) and diphenyl carbonate (DPC); b) simultaneously subjecting the plurality of at least substantially identical first
  • polycondensation reaction mixtures to conditions effective to result in a formation of a plurality of second polycondensation reaction mixtures, each comprising at least one polycondensation product; c) analyzing each of the plurality of second polycondensation reaction mixtures using near infrared spectroscopy to determine an absorbance spectrum of each of the plurality of second polycondensation reaction mixtures; d) determining a concentration of one or more components present in each of the plurality of second polycondensation reaction mixtures from each absorbance spectrum; and e) determining an intrinsic reactivity value of the single batch of polycondensation reactants from the determined concentration of the one or more components present in each of the plurality of second polycondensation reaction mixtures; wherein the components comprise BPA, DPC, phenol, or combinations thereof.
  • a system for determining an intrinsic reactivity value of a polycondensation reaction mixture comprising: a) a reaction unit comprising a plurality of reaction vessels; b) at least one dispensing unit for dispensing a single batch of polycondensation reactants into each of the plurality of reaction vessels such that each reaction vessel contains a substantially identical first polycondensation reaction mixture; c) a means for simultaneously subjecting each of the first polycondensation reaction mixtures to conditions effective to result in each first polycondensation reaction mixture forming a second polycondensation reaction mixture comprising a polycondensation product; d) a means for simultaneously subjecting each of the second polycondensation reaction mixtures to conditions effective to result in termination of the reaction; e) a near infrared spectrometer unit configured to analyze each second polycondensation reaction mixture and to determine an absorbance spectrum of each second polycondensation reaction mixture; and f) a computing device unit configured to
  • Aspect 42 The system of aspect 41, wherein the reaction unit comprises individual reaction vessels, multiple individual vessels arranged in a fixed configuration, or a plurality of individual vessels.
  • Aspect 43 The system according to any preceding aspect, wherein the reaction unit comprises an array.
  • Aspect 44 The system according to any preceding aspect, wherein the reaction unit comprises a first-order array, a second-order array, or a multi-order array, or combinations thereof.
  • Aspect 45 The system according to any preceding aspect, wherein the reaction unit comprises a multi-well microtiter plate.
  • Aspect 46 The system according to any preceding aspect, wherein the multi- well microtiter plate comprises a 96-well, 192- well, or 384-well microtiter plate.
  • Aspect 47 The system according to any preceding aspect, wherein the reaction vessels comprise glass or quartz vials.
  • Aspect 48 The system according to any preceding aspect, wherein the dispensing unit comprises a gravimetric dispensing system or a volumetric dispensing system.
  • Aspect 49 The system according to any preceding aspect, wherein the polycondensation reactants are dispensed in the reaction vessels simultaneously or
  • Aspect 50 The system according to any preceding aspect, wherein the means for simultaneously subjecting to conditions effective comprises an admixing unit.
  • Aspect 51 The system according to any preceding aspect, wherein the admixing unit shakes or agitates the reaction unit or reaction vessels to cause mixing of the polycondensation reactants.
  • Aspect 52 The system according to any preceding aspect, wherein the admixing unit comprises a means for stirring the plurality of polycondensation reaction mixtures.
  • Aspect 53 The system according to any preceding aspect, wherein the means for stirring comprises a plurality of stirring instruments.
  • Aspect 54 The system according to any preceding aspect, wherein each of the plurality of stirring instruments corresponds to a reaction vessel.
  • Aspect 55 The system according to any preceding aspect, wherein the means for simultaneously subjecting conditions effective comprise a temperature control unit.
  • Aspect 56 The system according to any preceding aspect, wherein the temperature control unit comprises a heating unit, or a cooling unit, or a combination thereof.
  • Aspect 57 The system according to any preceding aspect, wherein the heating unit comprises a heating element.
  • Aspect 58 The system according to any preceding aspect, wherein the heating element comprises a heat plate, heat lamp, or heating bath.
  • the cooling unit comprises a cooling element.
  • Aspect 60 The system according to any preceding aspect, wherein the cooling element comprises a refrigerated bath.
  • Aspect 61 The system according to any preceding aspect, wherein the near infrared spectrometer unit is configured to analyze a single reaction vessel.
  • Aspect 62 The system according to any preceding aspect, wherein the NTR spectrometer unit is configured to analyze a plurality of reaction vessels.
  • Aspect 63 The system according to any preceding aspect, wherein NIR spectrometer unit is configured to analyze the plurality of reaction vessels simultaneously or in parallel.
  • Aspect 64 The system according to any preceding aspect, wherein the NIR unit is configured to provide measured absorbance or spectroscopic data which are evaluated as described herein.
  • Aspect 65 The system according to any preceding aspect, wherein the NIR spectrometer unit is configured to irradiate each of the plurality of individual
  • polycondensation reaction mixtures with at least one wavelength of near infrared radiation and configured to determine the absorbance spectrum of each of the plurality of individual polycondensation reaction mixtures.
  • Aspect 66 The system according to any preceding aspect, wherein the absorbance spectrum measured by the NIR spectrometer unit comprises at least one wavelength in the range of from 800 nm to 2500 nm.
  • Aspect 67 The system according to any preceding aspect, wherein the absorbance spectrum comprises at least one wavelength in the range of from 1500 nm to 2000 nm.
  • Aspect 68 The system according to any preceding aspect, wherein absorbance spectrum comprises multiple wavelengths.
  • Aspect 69 The system according to any preceding aspect, wherein absorbance spectrum comprises an entire absorption band.
  • Aspect 70 The system according to any preceding aspect, wherein the computing device unit is configured to receive the determined absorbance spectrum data from the NIR spectroscopic unit, and configured to perform mathematical analysis of the determined absorbance spectrum to extract chemical information.
  • Aspect 71 The system according to any preceding aspect, wherein the chemical information comprises the concentration of at least one reaction component.
  • Aspect 72 The system according to any preceding aspect, wherein mathematical analysis comprises determining the concentration of at least one reaction component using the determined absorbance spectrum.
  • Aspect 73 The system according to any preceding aspect, wherein the computing device unit comprises computing hardware and software for performing mathematical analysis of the determined absorbance spectrum to extract chemical information.
  • Aspect 74 The system according to any preceding aspect, wherein the software performs one or more steps relating to application of mathematical analysis techniques to extract chemical information.
  • Aspect 75 The system according to any preceding aspect, wherein one wavelength of the absorbance spectrum is used to determine a concentration of at least one reaction component.
  • Aspect 76 The system according to any preceding aspect, wherein determining the concentration of at least one reaction component comprises univariate analysis.
  • Aspect 77 The system according to any preceding aspect, wherein multiple wavelengths are used to determine the concentration of at least one reaction component.
  • Aspect 78 The system according to any preceding aspect, wherein determining the concentration of at least one reaction components comprises multivariate analysis.
  • Aspect 79 The system according to any preceding aspect, wherein multivariate analysis comprises neural networks analysis, principal components analysis, partial least squares analysis, linear multivariate analysis, or nonlinear multivariate analysis.
  • Aspect 80 The system according to any preceding aspect, wherein determining an intrinsic reactivity comprises comparing the degree of conversion exhibited by a polycondensation reactant with the degree of conversion of a known reference sample tested in substantially the same reaction conditions.
  • Aspect 81 The system according to any preceding aspect, wherein the intrinsic reactivity is used to determine deactivation kinetics of the polycondensation reaction mixture.
  • Aspect 82 The system according to any preceding aspect, wherein the Gage repeatability and reproducibility (GRR) is less than or equal to 30%.
  • GRR Gage repeatability and reproducibility
  • Aspect 83 The system according to any preceding aspect, wherein the Gage repeatability and reproducibility (GRR) is less than or equal to 25%.
  • GRR Gage repeatability and reproducibility
  • Aspect 84 The system according to any preceding aspect, wherein the number of polycondensation reaction mixtures analyzed is sufficient to produce a predicted confidence interval of at least about 95%.
  • Aspect 85 The system according to any preceding aspect, wherein the number of polycondensation reaction mixtures analyzed is sufficient to produce a predicted confidence interval of at least about 98%.
  • Aspect 86 The system according to any preceding aspect, wherein at least a portion of the system is automated.
  • Aspect 87 The system according to any preceding aspect, wherein at least a portion of steps are performed by a robotic device.
  • Aspect 88 The system according to any preceding aspect, wherein at least a portion of the system is electrically powered.
  • reaction conditions e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions.
  • the samples described herein were prepared in a 250 milliliter (ml) three necked flask reactor.
  • the flask was charged with measured amounts of DPC and BPA.
  • the flask was sealed and placed in an oil bath.
  • the air in the headspace was exchanged multiple times using alternating cycles of vacuum and nitrogen filling.
  • the bath temperature was increased to 180 °C.
  • a timer was started to log reaction time. After a predetermined period, samples were taken and analyzed using the techniques and systems described herein.
  • High Performance Liquid Chromatography (HPLC) Analysis of the polycondensation reaction mixture samples described herein was performed using a Waters X-Terra C18 column (Waters, Milford, MA) with dimensions of 150 x 2.1 millimeters (mm) with 0.2% acetic acid (phase A) and acetonitrile (phase B) as the mobile phase. Gradient elution was as follows: 0 minutes (min) and 40% B, 3 min and 40% B, 40 min and 100% B and 45% and 100% B at a flow of 1 milliliters per minute (mL/min). The detector used was a UV- Visible diode array at a constant wavelength of 245 nm.
  • GRR ⁇ %) X 100, where o m is the standard deviation of a series of measurements conducted by different assays on the same sample and T is the tolerance of the measurement. When the number of samples used in the measurement is below 10, the standard deviation should be estimated by:
  • R avg is the average of the ranges in the measurements between assays and d* is a parameter which is a function of the number of assays and the number of samples used to conduct the repeatability test.
  • Example 1 the repeatability and variability of conventional reactivity tests were investigated.
  • the reactor was charged with 117.7 grams (g) of DPC and 114 g of BPA.
  • 0.6 ml of 0.001 N KOH solution was added, and placed in an oil bath. After 2 hours, samples were taken and measured using HPLC analysis.
  • Example 2 illustrates the estimated influence of the number of replicates on test variability.
  • a self-developed, first principles model for the simulation of the reaction system was designed using MATLAB as a software platform. Next, random noise was injected into the model in order to simulate the fit the lack of repeatability observed in the experimental results obtained in Example 1.

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Abstract

La présente invention concerne des procédés et des systèmes de détermination de la réactivité intrinsèque de réactifs de polycondensation à l'aide de spectroscopie en proche infrarouge et d'un criblage à haut débit. Cet abrégé est destiné à être utilisé comme outil de criblage à des fins de recherche dans la technique particulière et n'est pas destiné à être limitatif de la portée de la présente invention.
PCT/IB2014/061599 2013-05-23 2014-05-21 Procédé de détermination en discontinu de la réactivité intrinsèque de réactifs dans des réactions de polycondensation WO2014188359A1 (fr)

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US7786246B2 (en) 2007-10-18 2010-08-31 Sabic Innovative Plastics Ip B.V. Isosorbide-based polycarbonates, method of making, and articles formed therefrom

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CN106970173A (zh) * 2015-11-20 2017-07-21 日本株式会社日立高新技术科学 产生气体分析方法以及产生气体分析装置
CN109144470A (zh) * 2017-06-27 2019-01-04 上海寒武纪信息科技有限公司 一种计算装置及方法

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