EP1587852A1 - Polycarbonates et copolycarbonates cycliques, leur production et leur utilisation - Google Patents

Polycarbonates et copolycarbonates cycliques, leur production et leur utilisation

Info

Publication number
EP1587852A1
EP1587852A1 EP04700981A EP04700981A EP1587852A1 EP 1587852 A1 EP1587852 A1 EP 1587852A1 EP 04700981 A EP04700981 A EP 04700981A EP 04700981 A EP04700981 A EP 04700981A EP 1587852 A1 EP1587852 A1 EP 1587852A1
Authority
EP
European Patent Office
Prior art keywords
polycarbonates
hydroxyphenyl
copolycarbonates
bis
optionally
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04700981A
Other languages
German (de)
English (en)
Inventor
Rolf Wehrmann
Helmut-Werner Heuer
Claus-Ludolf Schultz
Hans-R. Kricheldorf
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP1587852A1 publication Critical patent/EP1587852A1/fr
Withdrawn legal-status Critical Current

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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
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • 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

  • the present invention relates to cyclic polycarbonates and copolycarbonates, processes for their preparation and their use for the production of certain products, and the products obtainable therefrom.
  • Aromatic polycarbonates belong to the group of engineering thermoplastics. They are characterized by the combination of the technologically important properties of transparency, heat resistance and toughness.
  • the alkali salts of bisphenols are reacted with phosgene in a two-phase mixture.
  • the molecular weight can be controlled by the amount of monophenols.
  • EP-A 0 827 948 describes a process in which mixtures of cyclic polycarbonates can be obtained starting from mixtures of special bischlorocarbonic acid esters.
  • the publication by DJ Brunelle, Polymer International 37 (1995) 179-186 describes how by hydrolysis / condensation reactions Cyclic oligomeric carbonates can be produced from aromatic bischloroformates.
  • Cyclic polycarbonates because of their better flowability than linear polycarbonates, are of particular interest for applications in which good flow of the polymer melt is desired, i.e. H. for example when injection molding complex structures.
  • the object was therefore to make cyclic polycarbonates and processes for their preparation available which avoid these disadvantages.
  • This object is surprisingly achieved by the polycarbonates or production processes according to the invention, in which cyclic polycarbonates or copolycarbonates can be obtained in one step, starting from bisphenols, without producing or isolating bischloroformic acid esters.
  • the invention relates to cyclic polycarbonates or copolycarbonates of the general formulas (Ia) and (Ib),
  • radical ODO or OEO stands for any diphenolate radicals in which -D - and -E- is an aromatic radical having 6 to 40 carbon atoms, the aromatic or one or more aromatic, optionally containing heteroatoms May contain cores and if necessary with or halogen is substituted and may contain aliphatic radicals, cycloaliphatic radicals, aromatic nuclei or heteroatoms as bridge members and in which k is an integer between 1 and 4000, preferably between 2 and 2000, particularly preferably between 2 and 1000 and very particularly preferably between 2 and 500 and particularly preferably between 2 and 300, m, n and o each independently represent numbers between 1 and 4000, preferably between ⁇ and 2000, particularly preferably between 1 and 1000 and very particularly preferably between 1 and 500 and particularly preferably between 1 and 300 stand.
  • Preferred structural units of the cyclic polycarbonates and copolycarbonates according to the invention are derived from general structures of the formula (2), the parenthesis describing the underlying diphenolate radicals in which R1 and R2 independently of one another are H, linear or branched -C-alkyl or alkoxy radicals, halogen such as Cl or Br or an optionally substituted aryl or aralkyl radical, preferably H or linear or branched C 1 -C 2 alkyl, particularly preferably H or C 8 alkyl radicals and very particularly preferably H or methyl,
  • X for a single bond, a Cj to Cg alkylene, C2 to Cs alkylidene, C5 to Cg cycloalkylidene radical which can be substituted by C1 to Cg alkyl, preferably methyl or ethyl radicals, or a Cg - to C ⁇ arylene residue, which may optionally be condensed with further heteroatoms containing aromatic rings, where p is an integer between 1 and 4000, preferably between 2 and 2000, particularly preferably between 2 and 1000 and very particularly preferably between 2 and 500 and in particular between 2 and 300.
  • the diphenola radicals in the formulas (Ia and B) and (2) are particularly preferably derived from the suitable diphenols mentioned below.
  • diphenols on which the general Foimel (2) are based are hydroquinone, resorcinol, dihydroxybiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) -thef, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, ⁇ , ⁇ '-bis (hydroxyphenyl) diisopropylbenzenes, and their kemalkylated and keml-halogenated compounds, and also ⁇ , ⁇ - bis (hydroxyphenyl) polysiloxanes naimt.
  • Preferred diphenols are, for example, 4,4'-dihydroxybi ⁇ henyl (DOD), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), l, l-bis (4-hydroxyphenyl) -3,3,5- trimethylcyclohexane (bisphenol TMC), l, l-bis (4-hydroxyphenyl) cyclohexane, 2,4-bis (4-hy droxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) -1 -phenylethane, 1, 1 -Bis- (4-hydroxyphenyl) -j-.
  • DOD 4,4'-dihydroxybi ⁇ henyl
  • bisphenol A 2,2-bis (4-hydroxyphenyl) propane
  • bisphenol TMC bisphenol TMC
  • l l-bis (4-hydroxyphenyl) cyclohexane
  • 2,4-bis (4-hy droxyphenyl) -2-methylbutane 1,
  • diphenols are, for example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 4,4'-dihydroxybiphenyl (DOD), 1,3-bis [2- (4-hydroxyphenyl) -2 propyl] benzene (bisphenol M), 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2- Bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ) -cyclohexane and l, l-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC).
  • bisphenol A 2,2-bis (4-hydroxyphenyl) propane
  • DOD 4,4'-dihydroxybiphenyl
  • 2,2-bis (4-hydroxyphenyl) -propane bisphenol A
  • 4,4'-dihydroxybiphenyl DOD
  • 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] are very particularly preferred.
  • -benzene bisphenol M
  • l, l-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane bisphenol TMC
  • the diphenols can be used both alone and in a mixture with one another; both homopolycarbonates and copolycarbonates are included.
  • the diphenols are known from the literature or can be prepared by processes known from the literature (see, for example, H. J. Buysch et al., Ullmann's Encyclopedia of Industrial Chemistry, VCH, New York 1991, 5th Ed., Vol. 19, p. 348).
  • Some of the compounds which can be used with three or more than three phenolic hydroxyl groups are, for example, phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hept-2-ene, 4,6-dimethyl-2, 4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4th -hydroxyphenyl) phenylmethane, 2,2-bis- [4,4-bis- (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis- (4-hydroxyphenylisopropyl) phenol, 2, 6-bis (2-hydroxy-5 '-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (3,4-dihydioxyphenyl) propane, hexa- [4- (4-
  • the present invention further relates to a Verfaliren for preparing cyclic polycarbonates and copolycarbonates of the formulas (la) and (lb), characterized in "that bisphenols are dissolved in aqueous alkaline solution, and simultaneously with, optionally dissolved in a solvent of carbonate into a two phase mixture of aqueous alkaline Solution of an organic solvent and a catalyst, preferably an amine compound, are added dropwise with stirring.
  • the bisphenols are in aqueous alkaline solution in concentrations of 0.05 to 15 wt .-%, preferably 0.05 to 12 wt .-%, particularly preferably 0.08 to 10 wt .-% and very particularly 0.08 to 8 wt .-% solved.
  • aqueous alkaline solution is in the context of this invention, both as a solvent for the bisphenols and as part of the two-phase mixture presented for a solution consisting of water in which at least one basic alkali or alkaline earth metal salt is dissolved.
  • Hydroxides in particular sodium and / or potassium hydroxides, are preferred.
  • concentration of the salts is in principle arbitrary, but is preferably between 0.1 and 20% by weight, particularly preferably between 0.1 and 18% by weight, very particularly preferably between 0.2 to 15% by weight and in particular very particularly preferably between 0.2 to 12% by weight.
  • the volume ratio of aqueous alkaline solution to organic solvent is 5:95 to 95: 5, preferably 20:80 to 80:20, particularly preferably 30:70 to 70:30 and very particularly preferably 40:60 to 60:40.
  • the molar ratio of bisphenol to phosgene is less than 1:10, preferably less than 1: 6, particularly preferably less than 1: 4 and very particularly preferably less than 1: 3.
  • the concentration of the cyclic according to the invention Polycarbonates and copolycarbonates in the organic phase is 0.1 to 20% by weight, preferably 0.3 to 12% by weight, particularly preferably 0.5 to 10% by weight and very particularly preferably 0.7 to 8% by weight .-%.
  • the concentration of the " amine compound, based on the amount of bisphenol used, is 0.1 to 10 mol%, preferably 0.2 to 8 mol%, particularly preferably 0.3 to 6 mol% and very particularly preferably 0.4 to 5 mol -%.
  • tetraalkylammonium salts are also suitable as catalysts; the suitable amounts of diphosgene are then calculated in accordance with the equivalents to the phosgene.
  • triphosgene When using triphosgene, tetraphenylphosphonium chloride is particularly suitable as a catalyst; the suitable amounts of triphosgene are then calculated in accordance with the equivalents to the phosgene.
  • Bisphenols are to be understood as the diphenols mentioned above, possibly with proportions of the above-mentioned branching agents.
  • the carbonate source is phosgene, diphosgene or triphosgene, preferably phosgene.
  • a solvent can optionally be dispensed with and the phosgene can be introduced directly into the reaction mixture.
  • tertiary amines such as triethylamine or N-alkylpiperidines ⁇ can be used.
  • Trialkylamines and 4- (dimethylämino) pyridine are suitable as catalysts.
  • Triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, N-methylpiperidine, N-ethylpiperidine and N-propylpiperidine are particularly suitable.
  • Small amounts of catalyst are advantageous for the cyclization, namely 0.2-25 mol%, particularly 0.5-5 mol%, very particularly 0.8-3 mol% (relative to the amount of diphenols).
  • Halogenated hydrocarbons such as methylene chloride and / or chlorobenzene, dichlorobenzene or trichlorobenzene or come as the organic solvent
  • the reaction temperature can be -5 ° C. to 200 ° C., preferably 0 ° C. to 120 ° C., particularly preferably 0 ° C. to 100 ° C. and very particularly preferably 5 ° C. to 80 ° C.
  • the molecular weights Mw of the cyclic polycarbonates and copolycarbonates according to the invention are in the range from 600 to 100,000 g / mol, preferably between 600 and 500,000 g / mol, particularly preferably between 600 and 250,000 g / mol and very particularly preferably between 600 and 120,000 g / mol and in particular between 600 and 80,000 g / mol (determined using GPC and polycarbonate calibration).
  • Preferred, particularly preferred or very particularly preferred are embodiments which make use of the parameters, compounds, definitions and explanations mentioned under preferred, particularly preferred or very particularly preferred or preferably etc..
  • cyclic polycarbonates and copolycarbonates according to the invention can be worked up in a known manner and processed into any shaped articles, for example by extrusion or injection molding.
  • the cyclic polycarbonates and copolycarbonates according to the invention can also contain other aromatic polycarbonates and / or other aromatic ones Polyester carbonates and / or other aromatic polyesters are admixed in a known manner.
  • thermoplastics such as fillers, UV stabilizers, thermal stabilizers, antistatic agents and pigments
  • these thermoplastics can also be added to the cyclic polycarbonates and copolycarbonates according to the invention; if necessary, the demolding behavior, the flow behavior and / or the flame resistance can be improved by adding external mold release agents, flow agents, and / or flame retardants (e.g. alkyl and aryl phosphites, phosphates, phosphines, low molecular weight carboxylic acid esters, halogen compounds, salts, chalk, Quartz powder, glass and carbon fibers, pigments and their combinations, such compounds are described, for example, in WO 99/55772, pp. 15-25, and in the corresponding chapters of the "Plastics Additives Handbook", ed. Hans Doubt, 5 th Edition 2000, Hanser Publishers, Kunststoff.).
  • the cyclic polycarbonates and copolycarbonates according to the invention can be processed into any shape / extrudate used wherever known polycarbonates, polyester carbonates and polyesters are used. Due to their property profile, they are particularly suitable as substrate materials for optical data storage such as CD, CD-R, DVD, or DVD-R, but can also be used, for example, as films in the electrical sector, as molded parts in vehicle construction and as plates for covers in the security area. Further possible applications of the polycarbonates according to the invention are:
  • Safety panes which are known to be required in many areas of buildings, vehicles and aircraft, and as shields for helmets.
  • polycarbonates with a content of glass fibers are used, which may additionally contain about 1-10% by weight MoS, based on the total weight.
  • optical device parts in particular lenses for photo and film cameras (see for example DE-A 2 701 173).
  • dialyzers For medical applications, e.g. Oxygenators, dialyzers.
  • the moldings and extrudates from the polymers according to the invention are also the subject of this application.
  • Example 2 u. a. Cycles of the masses 1269, 1360 and 1442, which are cyclic copolycarbonates from BPA and BP-TMC with different monomer ratios.
  • Example 3 u. a. Cycles of the masses 1618, 1660, 1701 and 1744, which are cyclic copolycarbonates from BPA and DOD with different monomer ratios.
  • a solution of bisphenol-A (20 mmol) and NaOH (120 mmol) in 200 mL water and a solution of diphosgene (20 mmol) in dry dichloromethane (200 mL) are stirred into a mixture of 50 mL water (contains 1 nmol NaOH) and 150 mL CH 2 C1 (contains 0.5 mmol triethylamine).
  • This Dripping should take about 1 hour and the temperature is kept in the range 19-21 ° C by occasional cooling with cold water.
  • the organic phase is then separated off, washed twice with water and dried with a little sodium sulfate. Then the organic phase is concentrated in a vacuum and the product is precipitated with methanol. Yield 60-75%. The yield depends on the type of phase separation in the washing processes and the amount of sodium sulfate.
  • the MALDI-TOF mass spectrum shows the peaks of cycles up to the measurement limit at 18 kDa. Below 3 kDa only tiny peaks of linear chains with two OH end groups appear. The amount of 2.5 mol% triethylamine relative to bisphenol-A was determined as the optimum for the cycle formation.

Abstract

La présente invention concerne des polycarbonates et des copolycarbonates cycliques, des procédés pour les produire, leur utilisation pour produire des produits définis, ainsi que les produits alors obtenus.
EP04700981A 2003-01-21 2004-01-09 Polycarbonates et copolycarbonates cycliques, leur production et leur utilisation Withdrawn EP1587852A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10302088A DE10302088A1 (de) 2003-01-21 2003-01-21 Cyclische Polycarbonate und Copolycarbonate, ihre Herstellung und Verwendung
DE10302088 2003-01-21
PCT/EP2004/000086 WO2004065454A1 (fr) 2003-01-21 2004-01-09 Polycarbonates et copolycarbonates cycliques, leur production et leur utilisation

Publications (1)

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EP1587852A1 true EP1587852A1 (fr) 2005-10-26

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EP04700981A Withdrawn EP1587852A1 (fr) 2003-01-21 2004-01-09 Polycarbonates et copolycarbonates cycliques, leur production et leur utilisation

Country Status (5)

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US (1) US20060089483A1 (fr)
EP (1) EP1587852A1 (fr)
CN (1) CN1738847A (fr)
DE (1) DE10302088A1 (fr)
WO (1) WO2004065454A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023149329A1 (fr) * 2022-02-07 2023-08-10 三菱ケミカル株式会社 Composition de résine de polycarbonate
CN115197410A (zh) * 2022-08-04 2022-10-18 南京工业大学 一种环状碳酸酯的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4644053A (en) * 1984-05-11 1987-02-17 General Electric Company Cyclic polycarbonate oligomers and methods for their preparation and use
JPH0625400A (ja) * 1992-07-07 1994-02-01 Idemitsu Kosan Co Ltd ポリカーボネート及びその製造方法
DE19636539A1 (de) * 1996-09-09 1998-03-12 Bayer Ag Gemische cyclischer Oligocarbonate, ihre Herstellung und Verwendung
EP0953605B1 (fr) * 1998-04-28 2004-09-15 Teijin Limited Composition de polycarbonate à écoulement amélioré
AU5982800A (en) * 1999-07-19 2001-02-05 Bayer Aktiengesellschaft Oligomeric bischlorocarbonic acid esters obtained from selected cycloaliphatic bisphenols and other bisphenols

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004065454A1 *

Also Published As

Publication number Publication date
CN1738847A (zh) 2006-02-22
US20060089483A1 (en) 2006-04-27
WO2004065454A1 (fr) 2004-08-05
DE10302088A1 (de) 2004-07-29

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