WO2000023499A1 - Continuous interfacial method for preparing aromatic polycarbonates - Google Patents
Continuous interfacial method for preparing aromatic polycarbonates Download PDFInfo
- Publication number
- WO2000023499A1 WO2000023499A1 PCT/US1999/014340 US9914340W WO0023499A1 WO 2000023499 A1 WO2000023499 A1 WO 2000023499A1 US 9914340 W US9914340 W US 9914340W WO 0023499 A1 WO0023499 A1 WO 0023499A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkali metal
- phosgene
- dihydroxyaromatic compound
- molar ratio
- carbonyl halide
- Prior art date
Links
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
-
- 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
Definitions
- This invention relates to the interfacial preparation of aromatic polycarbonates, and more particularly to their preparation by a continuous method.
- a well known method for polycarbonate preparation employs at least one dihydroxyaromatic compound, typically a bisphenol; a carbonyl halide, typically phosgene; a base, typically an alkali metal hydroxide, as an acid acceptor; a catalyst; and a substantially inert, substantially water- insoluble organic liquid such as methylene chloride.
- This method is frequently designated “interfacial” by reason of the interface existing between the distinct aqueous and organic phases.
- Interfacial polycarbonate preparation has, by and large, been a batch process although numerous disclosures of continuous processes exist in the art.
- US Patent 4,737,573 discloses a method adapted to continuous operation, wherein the first step is preparation of an intermediate product comprising polycarbonate oligomers, typically containing chloroformate end groups, in a tank reactor such as a continuous stirred tank reactor (CSTR).
- CSTR continuous stirred tank reactor
- This intermediate product may then be converted to high molecular weight polycarbonate in one or, if necessary, two downstream reactors.
- the first such reactor may be another CSTR and the second may be a limited back-mixing reactor; i.e., one approaching plug flow conditions.
- Copending application Serial No. 07/724,642 discloses a method for interfacial polycarbonate preparation which also involves an initial step of oligomer formation.
- the proportion of base (e.g., alkali metal hydroxide) employed therein is preferably equal to 2 + 4Y(Z - 1) moles of base per mole of dihydroxy compound, wherein Y is in the range of about 0-0.5 and Z is the number of "moles of carbonic acid derivative per mole of dihydroxy compound"; i.e., the molar ratio of carbonyl halide to dihydroxyaromatic compound.
- base e.g., alkali metal hydroxide
- Mw weight average molecular weight
- US Patent 5,359,117 discloses a continuous method for interfacial polycarbonate preparation in which an essential feature is maintenance of the ratio of equivalents of base to dihydroxyaromatic compound in the range of
- the molecular weight of the intermediate oligomer product unquestionably also has a significant effect on the properties of the high molecular weight polycarbonate ultimately formed in a continuous process. It has been found that if the oligomer molecular weight is too low, phosgenation efficiency may decrease, increasing raw material costs and necessitating very efficient scrubbing procedures to avoid discharge of very toxic phosgene into the atmosphere. In addition, low molecular weight oligomers tend to be less efficient at dissolving any unreacted dihydroxyaromatic compound, affording mixtures containing a solid phase which is difficult to process. On the other hand, oligomers of unduly high molecular weight produced in a continuous process can produce thermodynamically unstable polycarbonate products.
- the present invention is based in large part on the discovery that a major factor affecting thermodynamic stability of a continuously produced high molecular weight polycarbonate is the proportion of cyclic polycarbonate oligomers therein. Increasing the proportions of cyclic oligomers having degrees of polymerization below about 6 can have a very deleterious effect on thermodynamic stability. Moreover, the proportion of cyclic oligomers in the product has a direct relationship to the molecular weight of the oligomer intermediate.
- the invention is a method for preparing an aromatic polycarbonate which comprises:
- dihydroxyaromatic compounds useful in the method of this invention include those of the formula
- R is a divalent aromatic radical which may be an aromatic hydrocarbon or a substituted aromatic hydrocarbon radical, with illustrative substituents being alkyl, cycloalkyl, alkenyl (e.g., crosslinkable-graftable moieties such as allyl), halo (especially fluoro, chloro and /or bromo), nitro and alkoxy.
- the preferred R values have the formula
- each of A 1 and A 2 is a monocyclic divalent aromatic radical and Y is a single bond or a bridging radical in which one or two atoms separate A 1 from A 2 .
- the free valence bonds in formula II are usually in the meta or para positions of A 1 and A 2 in relation to Y.
- the A 1 and A 2 values may be unsubstituted phenylene or substituted derivatives thereof wherein the substituents are as defined for R. Unsubstituted phenylene radicals are preferred. Both A 1 and A 2 are preferably p-phenylene, although both may be o- or m-phenylene or one o- or m-phenylene and the other p-phenylene.
- the bridging radical, Y is one in which one or two atoms, preferably one, separate A 1 from A 2 . It is most often a hydrocarbon radical and particularly a saturated C1-12 aliphatic or alicyclic radical such as methylene, cyclohexylmethylene, [2.2.1]bicycloheptylmethylene, ethylene, ethylidene, 2,2-propylidene, l,l-(2,2-dimethylpropylidene), cyclohexylidene, cyclopentadecylidene, cyclododecylidene or 2,2-adamantylidene, especially an alkylidene radical.
- a hydrocarbon radical and particularly a saturated C1-12 aliphatic or alicyclic radical such as methylene, cyclohexylmethylene, [2.2.1]bicycloheptylmethylene, ethylene, ethylidene, 2,2-propylidene, l,
- Aryl-substituted radicals are included, as are unsaturated radicals and radicals containing atoms other than carbon and hydrogen; e.g., oxy groups. Substituents such as those previously enumerated may be present on the aliphatic, alicyclic and aromatic portions of the Y group.
- bisphenols Compounds containing radicals of formula II wherein Y is a bridging radical are classed as bisphenols.
- Illustrative bisphenols and other dihydroxyaromatic compounds for use in the invention are listed in the aforementioned US Patent 4,737,573, the disclosure of which is incorporated by reference herein.
- bisphenol will frequently be employed hereinafter, but it should be understood that other dihydroxyaromatic compounds may be substituted for all or part of the bisphenol when appropriate.
- the preferred bisphenols are those which are substantially insoluble in aqueous systems at temperatures within the range of 20-40°C and pH values in the range of about 1-5.
- bisphenols of relatively low molecular weight and high solubility in water such as resorcinol and hydroquinone
- Bisphenol A in which Y is isopropylidene and A 1 and A 2 are each p-phenylene is often especially preferred for reasons of availability and particular suitability for the purposes of the invention.
- bisphenol-based compounds containing ester linkages are also useful. These may be prepared, for example, by reacting two moles of bisphenol A with one mole of isophthaloyl or terephthaloyl chloride.
- a carbonyl halide preferably phosgene
- water and at least one substantially inert organic liquid are also employed in the method of the invention.
- the solubility of the bisphenol in the organic liquid is usually up to about 0.25 M at temperatures in the range of about 20-40°C, and preferably up to about 0.1 M.
- Said organic liquid should generally also be substantially insoluble in water.
- Illustrative liquids are aliphatic hydrocarbons such as hexane and n-heptane; chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane and 1,2-dichloroethylene; aromatic hydrocarbons such as benzene, toluene and xylene; substituted aromatic hydrocarbons such as chlorobenzene, o-dichlorobenzene, the chlorotoluenes, nitrobenzene and acetophenone; and carbon disulfide.
- the chlorinated aliphatic hydrocarbons, ' especially methylene chloride are preferred.
- alkali metal hydroxide (hereinafter sometimes simply "base” for brevity) and at least one interfacial polycarbonate formation catalyst.
- base an alkali metal hydroxide
- the alkali metal hydroxide is most often sodium hydroxide but may also be, for example, potassium hydroxide or mixtures of sodium hydroxide and potassium hydroxide.
- the catalyst may be a tertiary amine, typically a trialkylamine such as triethylamine or a highly nucleophilic heterocyclic amine such as 4- dimethylaminomorpholine, or a phase transfer catalyst, most often a quaternary ammonium salt such as tetra-t-butylammonium chloride or bromide or tetra-t-butylphosphonium chloride or bromide. Mixtures of such catalysts, especially mixtures of trialkylamines and tetraalkylammonium salts, may also be employed.
- a tertiary amine typically a trialkylamine such as triethylamine or a highly nucleophilic heterocyclic amine such as 4- dimethylaminomorpholine
- a phase transfer catalyst most often a quaternary ammonium salt such as tetra-t-butylammonium chloride or bromide or tetra-t-butylphosphonium
- a trialkylamine is employed as catalyst, either alone or in combination with a phase transfer catalyst. Therefore, the use of a phase transfer catalyst alone in this step is generally preferred.
- step A of the method of the invention the first stage of the reaction is conducted continuously under back-mixing conditions. This is most often achieved with the use of a tank reactor, especially a CSTR.
- the temperature in step A is generally in the range of about 15-50°C.
- the feeds for the first stage comprise an organic solution, two aqueous solutions and a gas or optionally liquid feed.
- the organic solution, in the organic liquid employed, includes catalyst and, preferably, a chain termination agent, most often a monohydroxyaromatic compound such as phenol or p-cumylphenol.
- the two aqueous solutions comprise, in one case, base and bisphenol, the latter existing in the form of its alkali metal salt; and in the other case, aqueous base alone in a proportion to provide the molar ratio of base to phosgene prescribed herein.
- the gas or optionally liquid feed is phosgene. Startup of the continuous first stage may be achieved in various ways.
- One is the preparation of an interfacial batch reaction mixture which is then phosgenated to a mole ratio of phosgene to bisphenol on the order of 0.8- 0.9:1, after which the CSTR containing the batch reaction mixture is continuously fed with the organic and aqueous phases.
- This procedure may have the disadvantage of producing a transient oligomer species of undesirably high molecular weight (weight average, Mw, whenever used herein), sometimes as high as about 10,000, as a result of a residence time which is atypically long in comparison to steady state continuous conditions.
- a preferred startup procedure is to charge the CSTR with an oligomer-containing reaction mixture typical of that from an earlier run.
- the two phases of an earlier mixture may thus be separated and the organic phase quenched with acid to inhibit further polymerization, and charged to the CSTR in combination with an aqueous brine (i.e., alkali metal halide solution, preferably sodium chloride) which may be the aqueous phase from an earlier reaction or a synthetically prepared brine of similar constitution.
- an aqueous brine i.e., alkali metal halide solution, preferably sodium chloride
- the organic, aqueous and gas or optionally liquid feeds previously described are then introduced at substantially constant rates. Flow rates are adjusted to produce the desired proportions of constituents based on bisphenol during the continuous process, which are preferably as follows, based on dihydroxy compound:
- a critical aspect of the invention is the molar ratio of base to phosgene. It is maintained at a value up to 1.8:1, preferably in the range of about 1.45-1.8:1 and most preferably in the range of about 1.6-1.8:1. Maintenance of this ratio in these ranges affords an intermediate oligomer product having a Mw up to about 6,000, preferably in the range of about 2,000-6,000 and most preferably in the range of about 4,000-6,000.
- the proportion of base employed according to the invention is not, as in the prior art, calculated primarily to maintain an established pH set point, but rather to maintain an established molar ratio with respect to phosgene. This will inherently afford a pH during the oligomer-forming reaction within the range of about 7.5-10.5.
- the product of step A is a two-phase aqueous-organic intermediate product mixture containing the desired polycarbonate oligomers in combination with by-products such as alkali metal halide, typically sodium chloride.
- step B said mixture is passed to a second stage for conversion to a final product comprising high molecular weight polycarbonate.
- the second stage may be conducted batchwise or continuously, in accordance with art-recognized procedures.
- Continuous conversion may employ a CSTR or similar back-mixed reactor, or a tube reactor of the type which usually operates under plug flow conditions.
- a catalyst mixture especially a mixture of phase transfer catalyst with trialkylamine in the respective amounts of about 0.1-1.0 and 0.2-1.0 mole percent based on bisphenol.
- a CSTR having a volume in the range of 900-1,000 ml was fitted with a metered gas inlet for phosgene, three liquid inlets, a condenser, a stirrer and a pH probe.
- the CSTR was initially charged with an organic phase reaction mixture from the steady state portion of an earlier reaction and a synthetic brine phase.
- the proportions of materials introduced were adjusted to provide in each example constant mole percentages of phosgene (104-110) and PCP (4.3-4.5) with respect to bisphenol A which, within these ranges, are not believed to materially affect the properties of the oligomeric intermediate product, and a constant mole percentage of TBAB with respect to bisphenol A in the range of abut 0.1-0.4.
- the residence time was 12 minutes, a constant molar ratio of sodium hydroxide to phosgene was maintained in each example and the phosgene flow rate was maintained at 5.9 or 6.6 g/min.
- the effluents from the CSTR was analyzed for polycarbonate oligomer molecular weight and for phosgene by-products, principally carbonates.
- the CSTR was charged with additional TBAB as necessary and with triethylamine to afford molar ratios of bisphenol A to TBAB and triethylamine of 200:1 and 200-400:1, respectively.
- the molecular weight building reaction was conducted under reflux and under batch conditions simulating a plug flow reactor.
- the resulting high molecular weight polycarbonates were isolated by precipitation into acetone and analyzed by high pressure liquid chromatography for cyclic oligomers having degrees of polymerization in the range of 3-6.
- Phosgenation efficiency is the amount in moles of phosgene actually incorporated in the oligomers divided by the amount actually fed. The amount actually incorporated is calculated from the levels of chloroformate and hydroxy end groups in the oligomers, taking into consideration the proportion of chain termination agent present. Comparison in the table is made with five controls (Cl-5) run under similar conditions and a sixth control (C6) which was prepared under batch conditions, using 10% excess phosgene relative to bisphenol A.
- Examples 1-3 in which the molar ratio of base to phosgene was below 1.8:1 and specifically in the range of 1.45-1.8:1, afforded oligomers having molecular weights up to 6,000 and specifically within the desired range of 2,000-6,000. They also afford polycarbonate products having lower proportions of cyclic oligomers than Controls 1-5, in which higher ratios of base to phosgene were employed.
- Controls 1-5 A comparison of Examples 1-3 and Controls 1-5 with Control 6 shows the dependency of cyclic oligomer content on base to phosgene ratio in continuous but not in batch processes.
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- Health & Medical Sciences (AREA)
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- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69917667T DE69917667T2 (en) | 1998-10-22 | 1999-06-24 | CONTINUOUS INTERMEDIATE PROCESS FOR DISPLAYING AROMATIC POLYCARBONATE |
JP2000577220A JP3448278B2 (en) | 1998-10-22 | 1999-06-24 | Method for producing continuous interface of aromatic polycarbonate |
EP99930679A EP1123339B1 (en) | 1998-10-22 | 1999-06-24 | Continuous interfacial method for preparing aromatic polycarbonates |
HK02105072A HK1043377A1 (en) | 1998-10-22 | 2002-07-08 | Continuous interfacial method for preparing aromatic polycarbonates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/177,023 US5973103A (en) | 1998-10-22 | 1998-10-22 | Continuous interfacial method for preparing aromatic polycarbonates |
US09/177,023 | 1998-10-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000023499A1 true WO2000023499A1 (en) | 2000-04-27 |
Family
ID=22646863
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/014340 WO2000023499A1 (en) | 1998-10-22 | 1999-06-24 | Continuous interfacial method for preparing aromatic polycarbonates |
Country Status (8)
Country | Link |
---|---|
US (1) | US5973103A (en) |
EP (1) | EP1123339B1 (en) |
JP (1) | JP3448278B2 (en) |
KR (1) | KR100545426B1 (en) |
CN (1) | CN1207321C (en) |
DE (1) | DE69917667T2 (en) |
HK (1) | HK1043377A1 (en) |
WO (1) | WO2000023499A1 (en) |
Cited By (1)
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JP2005521765A (en) * | 2002-03-25 | 2005-07-21 | ゼネラル・エレクトリック・カンパニイ | Synthesis of copolyestercarbonate |
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GB0016354D0 (en) * | 2000-07-03 | 2000-08-23 | Optaglio Ltd | Optical security device |
US6303737B1 (en) | 2001-01-12 | 2001-10-16 | General Electric Company | Melt polycarbonate catalyst systems |
US6323304B1 (en) | 2001-01-12 | 2001-11-27 | General Electric Company | Melt polycarbonate catalyst systems |
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US6376640B1 (en) | 2001-01-12 | 2002-04-23 | General Electric Company | Melt polycarbonate catalyst systems |
US6291631B1 (en) | 2001-01-12 | 2001-09-18 | General Electric Company | Melt polycarbonate catalyst systems |
US6323303B1 (en) | 2001-03-01 | 2001-11-27 | General Electric Company | Melt polycarbonate catalyst systems |
US6620939B2 (en) * | 2001-09-18 | 2003-09-16 | General Electric Company | Method for producing bisphenol catalysts and bisphenols |
US6583258B1 (en) | 2001-10-25 | 2003-06-24 | General Electric Company | Salts of organic phosphates as catalysts for melt polycarbonate |
US6610814B2 (en) | 2001-10-25 | 2003-08-26 | General Electric Company | Compounds of antimony and germanium as catalysts for melt polycarbonate |
US6608164B2 (en) | 2001-10-25 | 2003-08-19 | General Electric Company | Salts of heterocyclic diols as catalysts for melt polycarbonate |
KR101102637B1 (en) * | 2003-02-21 | 2012-01-04 | 사빅 이노베이티브 플라스틱스 아이피 비.브이. | Transparent and high-heat polycarbonate-polysiloxane copolymers and transparent blends with polycarbonate and a process for preparing same |
DE102004061754A1 (en) * | 2004-12-22 | 2006-07-06 | Bayer Materialscience Ag | Substrate materials for transparent injection molded parts |
DE102004061714A1 (en) * | 2004-12-22 | 2006-07-20 | Bayer Materialscience Ag | Polycarbonates with good wettability |
DE102004061713A1 (en) * | 2004-12-22 | 2006-07-20 | Bayer Materialscience Ag | Polycarbonates with good wettability |
US7549320B2 (en) * | 2007-01-11 | 2009-06-23 | Halliburton Energy Services, Inc. | Measuring cement properties |
DE102008008842A1 (en) * | 2008-02-13 | 2009-08-27 | Bayer Materialscience Ag | Alkylphenol for molecular weight adjustment and polycarbonate compositions having improved properties |
CN102775592B (en) * | 2012-03-12 | 2014-06-18 | 甘肃银光聚银化工有限公司 | Method for continuously preparing makrolon by phosgene interface polycondensation |
CN114653330B (en) * | 2022-03-30 | 2023-08-11 | 西安近代化学研究所 | Device and process for dynamically and continuously preparing polycarbonate |
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1998
- 1998-10-22 US US09/177,023 patent/US5973103A/en not_active Expired - Lifetime
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1999
- 1999-06-24 EP EP99930679A patent/EP1123339B1/en not_active Expired - Lifetime
- 1999-06-24 WO PCT/US1999/014340 patent/WO2000023499A1/en active IP Right Grant
- 1999-06-24 CN CNB998147028A patent/CN1207321C/en not_active Expired - Fee Related
- 1999-06-24 DE DE69917667T patent/DE69917667T2/en not_active Expired - Fee Related
- 1999-06-24 KR KR1020017004942A patent/KR100545426B1/en not_active IP Right Cessation
- 1999-06-24 JP JP2000577220A patent/JP3448278B2/en not_active Expired - Lifetime
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2002
- 2002-07-08 HK HK02105072A patent/HK1043377A1/en not_active IP Right Cessation
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EP0000753A1 (en) * | 1977-08-09 | 1979-02-21 | Bayer Ag | Process for the preparation of polycarbonates and the polycarbonates obtained |
US4535143A (en) * | 1984-08-06 | 1985-08-13 | Mobay Chemical Corporation | Process for the preparation of copolycarbonates of sulfonyl diphenol |
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JP2005521765A (en) * | 2002-03-25 | 2005-07-21 | ゼネラル・エレクトリック・カンパニイ | Synthesis of copolyestercarbonate |
Also Published As
Publication number | Publication date |
---|---|
US5973103A (en) | 1999-10-26 |
KR100545426B1 (en) | 2006-01-24 |
CN1207321C (en) | 2005-06-22 |
JP3448278B2 (en) | 2003-09-22 |
EP1123339B1 (en) | 2004-05-26 |
DE69917667T2 (en) | 2005-06-02 |
EP1123339A1 (en) | 2001-08-16 |
CN1331713A (en) | 2002-01-16 |
KR20010080259A (en) | 2001-08-22 |
JP2002527590A (en) | 2002-08-27 |
DE69917667D1 (en) | 2004-07-01 |
HK1043377A1 (en) | 2002-09-13 |
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