Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31507—Of polycarbonate

Definitions

• the present invention relates to the use of stress-crack-resistant, impact-resistant copolycarbonates with particularly good low-temperature properties and good aging stability, for applications in which particularly good low-temperature properties and / or high aging stability are required, e.g. for automotive or outdoor applications, as well as new copolycarbonates themselves.
• Polycarbonates typically become brittle at low temperatures, i.e. they tend to break and lose their impact strength.
• polycarbonates After storage at temperatures below the glass transition temperature, polycarbonates also show an aging effect that is dependent on the storage time and temperature, which significantly reduces the high energy level in the impact strength (Bottenbruch et al., Engineering Thermoplastics Polycarbonates, Polyacetals, Polyesters, Cellulose Esters, Carl Hanser Verlag Kunststoff, Vienna, New York, 1996,
• Copolycarbonates based on 4,4'-dihydroxydiphenyl and 2,2-bis (4-hydroxy ⁇ henyl) propane have now been known from JP 5 117 382 and in EP-AI 0 544407, US 5 470 938, US 5 532 324 and No. 5,401,826 is described as particularly chemical-resistant, heat-resistant and flame-retardant, with, in comparison to commercially available polycarbonate made from pure bisphenol, the same mechanical properties and transparency.
• these copolycarbonates have particularly good low-temperature properties, let alone that these polycarbonates have a particular aging stability.
• the task was therefore to find a transparent polycarbonate which, on the one hand, shows improved low-temperature toughness compared to polycarbonate made from pure 2,2-bis (4-hydroxyphenyl) propane, and on the other hand has increased aging stability with improved stress cracking behavior.
• the copolycarbonate according to the invention shows no aging effect which is dependent on the storage time and temperature when stored below the glass transition temperature of the copolycarbonate, so that the high energy level in the impact strength is maintained and the polycarbonates do not become brittle.
• the copolycarbonate according to the invention thus provides a material which has very good notched impact strength at low low temperatures, but which also does not lose this property again due to aging effects due to storage at temperatures below the glass transition temperature.
• the present invention therefore relates to the use of copolycarbonates which, from 0.1 mol% to 46 mol%, preferably from 11 mol% to 34 mol% and in particular from 26 mol% to 34 mol%, of compounds of the formula (I),
• R 1 to R 4 independently of one another are H, C 1 -C 4 -alkyl, phenyl, substituted phenyl or halogen, preferably H, C 1 -C 4 -alkyl or halogen and particularly preferably all the same radical, in particular H or tert-butyl stand, and complementary amounts, ie 99.9 mol% to 54 mol%, preferably 89 mol% to 66 mol% and in particular 74 mol% to 66 mol% of compounds of the formula (II)
• R 5 - R 8 are independently H, CH 3, Cl or Br, and X is C ⁇ -C 5 alkylene, C 2 -C 5 alkylidene, C 5 -C 6 cycloalkylene, C 5 -C ⁇ 0 cycloalkylidene is , are built up as monomers, as materials in areas where particularly good low-temperature properties and thermal stability are required.
• Copolycarbonates composed of 34-26 mol%, especially 33-27 mol%, in particular 32-28 mol%, very particularly 31-29 mol% and particularly highlighted 30 mol% of monomer of formula (I) are very particularly preferred and even subject matter of the invention. , each supplemented by a complementary content of monomer of formula (II).
• the percentages of the bisphenol monomers relate to the total content of bisphenols defined in the polycarbonates at 100%.
• a pure bisphenol A polycarbonate would then consist of 100% bisphenol A.
• the carbonate content from carbonic acid esters or halides is not taken into account.
• Preferred, particularly preferred or very particularly preferred are polycarbonates which have the compositions mentioned under preferred, particularly preferred or very particularly preferred.
• copolycarbonates on the one hand have particularly good low-temperature properties and on the other hand also have particularly good aging properties. They can therefore be used as moldings wherever the properties of the polycarbonates known hitherto are insufficient, in particular, for. B. in the electrical sector and in the construction sector, for covers or glazing, in particular in the automotive sector as films, plates, fittings or housing parts, but also in the optical field as lenses and data storage as well as consumer goods, when increased heat resistance or chemical resistance with good low-temperature properties and / or aging stability at the same time. In addition, they can also replace other materials in which ordinary polycarbonates have not been able to be used because of their insufficient low-temperature properties.
• Good low-temperature properties are to be understood according to the invention as good, but not restrictive, good low-temperature toughness, since ordinary polycarbonates break brittle at low temperatures in the impact test.
• low temperatures are understood to mean temperatures below -10 ° C, particularly preferably below -20 ° C, particularly preferably below -30 ° C, very particularly preferably below -40 ° C, in particular below -50 ° C.
• good thermal stability and aging stability is to be understood, by way of example, but not restrictively, to mean good notched impact strength after annealing, since ordinary polycarbonates become brittle after annealing and thus tend to break and crack.
• Glass transition temperature of 155 ° C to understand preferably the temperature is range from 40 ° C to 140 ° C, particularly preferably from 60 ° C to 140 ° C and very particularly preferably from 80 ° C to 140 ° C.
• Preferred compounds of formula (I) are 4,4'-dihydroxydiphenyl (DOD) and 4,4'-dihydroxy-3,3 ', 5,5'tetra (tert-butyl) diphenyl, 4,4'-dihydroxy- 3,3 ', 5,5'tetra (n-butyl) diphenyl and 4,4'-dihydroxy-3,3', 5,5'tetra (methyl) diphenyl, 4,4'-dihydroxydiphenyl is particularly preferred.
• DOD 4,4'-dihydroxydiphenyl
• DOD 4,4'-dihydroxy-3,3 ', 5,5'tetra (tert-butyl) diphenyl
• 4,4'-dihydroxy- 3,3 ', 5,5'tetra (n-butyl) diphenyl 4,4'-dihydroxy-3,3', 5,5'tetra (methyl) diphenyl
• 4,4'-dihydroxydiphenyl is particularly preferred.
• Preferred compounds of the formula (II) are 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 1,3-bis [2- (4- hydroxyphenyl) -2-propyl] benzene, 1,1-bis (4-hydroxyphenyl) -1-phenyl ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, in particular 2,2-bis (4-hydroxyphenyl) propane (Bisphenol A) and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC), very particularly preferably 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).
• both a compound of the formula (II), with formation of binary copolycarbonates, and also a plurality of compounds of the formula (II) can be used.
• the starting materials of the formula (I) and (II) can of course contain impurities due to the synthesis.
• a high level of purity is desirable and desirable, which is why these educts are used with the highest possible level of purity.
• polycarbonates and copolycarbonates are generally known in the literature and is also carried out accordingly in the cases according to the invention: According to DE-OS 2 119 779, the production of polycarbonates with the participation of monomers of the formula (I) is preferably carried out in solution, specifically by the phase interface process and the process in homogeneous phase.
• melt transesterification process acetate processes and phenyl ester processes
• transesterification processes acetate processes and phenyl ester processes
• the copolycarbonates can have molecular weights between Mw (weight average
• Molecular weight 10,000 to 60,000, preferably Mw 20,000 to 55,000, determined by measuring the relative solution viscosity in dichloromethane or in mixtures of equal amounts by weight of phenol / o-dichlorobenzene, calibrated by light scattering.
• the polycarbonates according to the invention can be processed thermoplastically in the usual manner at temperatures of 240 ° C. to 380 ° C., preferably 260 ° C. to 360 ° C. Any shaped bodies and foils can be produced in a known manner by injection molding or via extrusion. Moldings and extrudates from the copolycarbonates according to the invention are also the subject of the present application.
• the polycarbonates according to the invention are readily soluble in solvents such as chlorinated hydrocarbons, for example methylene chloride, and can thus be processed, for example, to give cast films in a known manner.
• Safety windows which are known to be required in many areas of buildings, vehicles and aircraft, and as shields for helmets.
• polycarbonates with a glass fiber content are used, which may additionally contain about 1-10% by weight of MoS 2 , based on the total weight.
• optical device parts in particular lenses for photo and film cameras (see for example DE-OS 2 701 173).
• Headlight lamps so-called “head lamps” or scattered light discs.
• dialyzers For medical applications, e.g. Oxygenators, dialyzers.
• films can be made from the high molecular weight aromatic polycarbonates of the invention.
• the films have preferred thicknesses between 1 and 1500 ⁇ m, in particular preferred thicknesses between 10 and 900 ⁇ m.
• the films obtained can be stretched monoaxially or biaxially in a manner known per se, preferably in a ratio of 1: 1.5 to 1: 5.
• the films can be produced by the known processes for film production, for example by extrusion of a polymer melt through a slot die, by blowing on a film blowing machine, by deep drawing or casting. It is possible that the foils are used on their own. They can of course also be used to produce composite films with other plastic films using the conventional methods, with all known films in principle being suitable as partners, depending on the desired application and the end property of the composite film. A composite of two or more foils can be created.
• the copolycarbonates according to the invention can also be used in other layer systems, for example in coextruded sheets.
• the polycarbonates according to the invention can contain different end groups. These are introduced by chain breakers. Chain terminators in the sense of the invention are those of the formula (III)
• R, R 'and R independently of one another H, optionally branched Cj-C 4 -
• the polycarbonates can contain small amounts of 0.02 to 3.6 mol% (based on the
• Suitable branching agents are the compounds with three or more functional groups suitable for polycarbonate production, preferably those with three or more than three phenolic OH groups, for example branching agents, as mentioned in EP-A 708 130, p. 4, preferably 1 , 1,1-tri- (4-hydroxyphenyl) ethane and isatin biscresol.
• auxiliaries and reinforcing materials can be added to the polycarbonates according to the invention.
• thermal and UV stabilizers flow aids, mold release agents, flame retardants, pigments, finely divided minerals, fiber materials, e.g. Alkyl and
• Such compounds are described, for example, in WO 99/55772, pp. 15-25, and in "Plastics Additives", R. Gumbleter and H. Müller, Hanser Publishers 1983.
• polystyrene can also be mixed into the polycarbonates according to the invention, e.g. Polyolefins, polyurethanes, polyesters, acrylonitrile butadiene styrene and polystyrene.
• These substances are preferably added to the finished polycarbonate in conventional units, but, depending on the requirements, can also be carried out at a different stage in the production process.
• the impact test according to ISO 180 / 4A was used to determine the impact strength.
• a polycarbonate with 30 mol% dihydroxydiphenyl (DOD) and 70 mol% bisphenol A was produced in the phase interface process.
• Tert-butylphenol was used as the chain terminator.
• the granules have a relative solution viscosity of
• a polycarbonate with 30 mol% DOD and 70 mol% bisphenol A was produced in the melt transesterification process.
• the product has a relative solution viscosity of 1.28.
• a polycarbonate with 35 mol% DOD and 65 mol% bisphenol A was produced in the melt transesterification process.
• the product has a relative solution viscosity of 1.295.
• the product has a relative solution viscosity of 1.295.
• a polycarbonate with 20 mol% DOD and 80 mol% bisphenol A was produced in the melt transesterification process.
• the product has a relative solution viscosity of 1.295.
• Table 2 shows the superior low-temperature toughness of the inventive copolycarbonates of Examples 1-3 at -60 ° C.
• the property profile of the copolycarbonate according to the invention also changed significantly after aging.
• polycarbonate from pure bisphenol A shows brittle fracture behavior, while the tough behavior of the copolycarbonate can still be observed after 7 days.
• the copolymer shows tough fracture behavior at a high level even after storage at 150 ° C. and subsequent impact test.

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• 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)
• Compositions Of Macromolecular Compounds (AREA)
• Saccharide Compounds (AREA)

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• 2000
  • 2000-09-26 DE DE2000147483 patent/DE10047483A1/de not_active Withdrawn
• 2001
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  • 2001-09-13 AU AU2001291859A patent/AU2001291859A1/en not_active Abandoned
  • 2001-09-13 KR KR1020037004283A patent/KR100845647B1/ko not_active IP Right Cessation
  • 2001-09-13 EP EP01972054A patent/EP1325056A1/de not_active Withdrawn
  • 2001-09-13 WO PCT/EP2001/010562 patent/WO2002026862A1/de not_active Application Discontinuation
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  • 2001-09-13 JP JP2002531240A patent/JP2004510040A/ja active Pending
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• 2002
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