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WO2002046270A1 - Polycarbonates hautes temperatures a tenacite amelioree et procede de fabrication correspondant - Google Patents

Polycarbonates hautes temperatures a tenacite amelioree et procede de fabrication correspondant Download PDF

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Publication number
WO2002046270A1
WO2002046270A1 PCT/US2001/031901 US0131901W WO0246270A1 WO 2002046270 A1 WO2002046270 A1 WO 2002046270A1 US 0131901 W US0131901 W US 0131901W WO 0246270 A1 WO0246270 A1 WO 0246270A1
Authority
WO
WIPO (PCT)
Prior art keywords
bpt
mol
bisphenol
residues
bpa
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.)
Ceased
Application number
PCT/US2001/031901
Other languages
English (en)
Inventor
James Alan Mahood
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.)
General Electric Co
Original Assignee
General Electric Co
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 General Electric Co filed Critical General Electric Co
Priority to AU2002216623A priority Critical patent/AU2002216623A1/en
Publication of WO2002046270A1 publication Critical patent/WO2002046270A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C08G64/20—General preparatory processes
    • C08G64/22—General preparatory processes using carbonyl halides
    • C08G64/24—General preparatory processes using carbonyl halides and phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation

Definitions

  • This application relates to high heat polycarbonates, and to methods and compositions useful in making same.
  • Polycarbonates are a well known class of high impact resistant thermoplastic resins characterized by optical clarity, high ductility as well as other advantageous properties. They are frequently employed as lenses and windows as a result of their transparency.
  • Bisphenol A (BPA) polycarbonate is the predominant commercially available resin of this type. It is derived from 2,2-bis(4- hydroxyphenyl)propane and ordinarily has a glass transition temperature of about 150 °C.
  • polycarbonates which, while retaining the ductility of BPA, have higher glass transition temperatures and are therefore more resistant to softening when heated.
  • Polycarbonates possessing increased glass transition temperatures are very desirable, for instance, in the automotive and aircraft industries. Particularly, they may be used in the preparation of automotive headlamp lenses which are becoming smaller in size and characterized by closer proximity of the lenses to the heat- generating light source.
  • the invention provides a method for making polycarbonate comprising copolymerizing BPA with BPT- 1 and BPT-2.
  • the resulting polycarbonate is thus a terpolymer of BPA/BPT- l/BPT-2, where the BPA preferably makes up at least 20 mol% of the polymer.
  • the BPT-1 and BPT-2 are suitably added to the BPA during the reaction as a mixture.
  • This teipolymer suitably contains BPT-1 and BPT-2 in a ratio, BPT-l/BPT-2, in the range of 70/30 to 10/90, preferably less than or equal to 50/50, for example around 30/70.
  • Fig. 1 shows the structure of a type of phenol useful in making polycarbonates in accordance with the invention.
  • the present invention provides polycarbonate copolymers having increased glass transition temperatures, a method for making such copolymers, and a mixture which can be used in the method.
  • the polycarbonate copolymers of the invention comprise copolymerized residues of BPA, BPT-1 and BPT-2.
  • the BPA is suitably present in amounts in excess of 20 mol %, for example 20-75 mol%, preferably 35 to 50 mol %.
  • the balance of the polycarbonate is BPT- 1 and BPT-2 residues.
  • the ratio of BPT-l/BPT-2 is in the range of 70/30 to
  • BPT-1 and BPT-2 are isomers and that they therefore have the same molecular weight. Thus, the ratio of BPT-1 to BPT-2 is the same, whether it is on a molar or weight basis).
  • the polycarbonate of the invention may also include residues of additional dihydric phenol comonomers known for use in the production of polycarbonates, including but not limited to those phenols which can be employed in the synthesis of polycarbonates having the general formula as shown in Fig. 1, where R15 is selected independently from the group consisting of H and C]-C 3 alkyl, and R 16 and R17 are independently O-C ⁇ alkyl or aryl.
  • these additional comonomers will be limited to amounts of less than 20% by weight.
  • the polycarbonate copolymers of the invention can be prepared by an interfacial process in which the BPA, BPT-1 and BPT-2 are solubilized in a solvent system and then exposed to phosgene in the presence of a base. The resulting polymer is recovered from the brine layer, washed with acid, and may then be further recovered by conventional methods such as steam precipitation and drying.
  • the polycarbonate copolymers of the invention can also be prepared using the indicated comonomers by other techniques known in the art including melt polymerizations (transesterification) for example as described in U.S. Patents Nos. 4,948,871, 5,204,377 and 5,214,073 and bischloroformate/oligomerization reactions for example as described in US
  • Bisphenol A (5396g, 23.6 mol) and a 30/70 mixture of BPT1/BPT2 (3602g, 11.1 mol) were charged to a 100L agitated reactor along with methylene chloride (39L), water (19L), triethylamine (48 ml) and p- cumylphenol (221 g).
  • Phosgene 4020 g, 40.6 mol was added at 150 g/min rate while the pH was held at 10.0-10.50 by controlled addition of a 50% caustic solution.
  • the resulting polymer solution was separated from the brine layer, washed with dilute HCl solution, and then washed with water until the level of titratable chloride was less than 3 ppm.
  • the polymer was precipitated with steam and dried.
  • the resulting resin was a molecular weight of 30,400 by GPC, a Tg of 177 °C and a 23 °C notched izod impact strength of 11.8 ft- lb/in.
  • Example 2 The procedure of Example 1 was repeated except that BPA was added at a level of 75 mol% instead of 68 mol %.
  • the resulting polymer had a molecular weight of 30,100 by GC, a Tg of 169 °C and a 23 °C notched izod impact of 12.9 ft-lb/in. Comparative Example
  • BPA at various concentrations from 30 to 50 mol % and end-cap levels.
  • the measured values for Tg ranged from 169 to 195 °C and for 23 °C notched izod impact energy ranged from 5.8 to 10.1 ft-lbs/in.
  • the notched izod impact energy of the copolymers made with BPT-2 was less than the values observed using the combination of BPT-1 and BPT-2 in accordance with the invention.
  • the highest observed notched izod value was 8.8 ft- lbs/in, a value which is substantially below that observed for the compositions of examples 1 and 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne des copolymères de bisphénol A (BPA), BPT-1 et BPT-2 à températures de transition vitreuse élevées présentant toutefois une ductilité, une clarté et une résistance au fissurage latéral bonnes. Ainsi, le polycarbonate est fabriqué par copolymérisation de BPA avec du BPT-1 et du BPT-2. Le polycarbonate qui en résulte est un copolymère triple de BPA/BPT-1/BPT-2, dans lequel le BPA représente, de préférence, au moins 20 % en moles de polymère. Ce copolymère triple contient du BPT-1 et du BPT-2 dans une proportion, BPT-1/BPT-2, comprise entre 70/30 et 10/90, et, de préférence, inférieure ou égale à 50/50, par exemple environ 30/70.
PCT/US2001/031901 2000-12-08 2001-10-10 Polycarbonates hautes temperatures a tenacite amelioree et procede de fabrication correspondant Ceased WO2002046270A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002216623A AU2002216623A1 (en) 2000-12-08 2001-10-10 High heat polycarbonates with improved toughness and method for making same

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US25439700P 2000-12-08 2000-12-08
US25435900P 2000-12-08 2000-12-08
US25435700P 2000-12-08 2000-12-08
US60/254,359 2000-12-08
US60/254,397 2000-12-08
US60/254,357 2000-12-08
US68137701A 2001-03-27 2001-03-27
US09/681,377 2001-03-27

Publications (1)

Publication Number Publication Date
WO2002046270A1 true WO2002046270A1 (fr) 2002-06-13

Family

ID=27500504

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/031901 Ceased WO2002046270A1 (fr) 2000-12-08 2001-10-10 Polycarbonates hautes temperatures a tenacite amelioree et procede de fabrication correspondant

Country Status (2)

Country Link
AU (1) AU2002216623A1 (fr)
WO (1) WO2002046270A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5480959A (en) * 1993-05-17 1996-01-02 General Electric Company Substantially pure bisphenols and polymers comprising bisphenols
EP0982340A1 (fr) * 1998-03-17 2000-03-01 Teijin Limited Procede de production de polycarbonate aromatique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5480959A (en) * 1993-05-17 1996-01-02 General Electric Company Substantially pure bisphenols and polymers comprising bisphenols
EP0982340A1 (fr) * 1998-03-17 2000-03-01 Teijin Limited Procede de production de polycarbonate aromatique

Also Published As

Publication number Publication date
AU2002216623A1 (en) 2002-06-18

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