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
  • C08G64/30—General preparatory processes using carbonates
  • C08G64/307—General preparatory processes using carbonates and phenols

Definitions

• Polycarbonates produced using the melt polymerization process contain multifunctional structural units, are highly branched and have a pronounced non-Newtonian flow behavior.
• the inevitable generation of multifunctional branching structural units during the polymerization is known and is described, for example, in Angewandte Chemie 20, pp. 633-660, 1956. Because of the different flow properties, it is difficult to use these two types of polycarbonates in an interchangeable manner, for example in injection molding or extrusion processes ,
• Typical melt-polymerized polycarbonate contains branching units, which lead to a pronounced, non-Newtonian flow behavior that usually is qualified by the shear thinning ratio. Unfortunately, the branching also leads to an unacceptable yellow color.
• the object of the invention is to produce a melt-polymerized polycarbonate with theological properties which are comparable to those of an interface-polymerized polycarbonate, these polycarbonates should have an excellent color and color stability.
• the polycarbonate according to the invention produced by melt polymerization (transesterification process), contains branchable multifunctional structural units and nevertheless has a low non-Newtonian flow behavior which is equivalent to the linear polycarbonates produced by interfacial polymerization. This is surprising because all previous melt-polymerized polycarbonates have a much more pronounced non-Newtonian flow behavior than linear polycarbonates.
• the polycarbonates according to the invention show excellent color stability during injection molding.
• melt-polymerized polycarbonates according to the invention correspond to the general formula (1)
• Suitable di-C ö -C ⁇ -aryl esters also include unsymmetrical diaryl esters which contain a mixture of aryl substituents. Most preferred are phenylcresyl carbonate and 4-tert-butylphenylphenyl carbonate.
• a branching agent may be added, such as compounds containing three functional phenolic OH groups. This would obviously branch the polymer and would increase the non-Newtonian flow behavior of the polymer.
• Suitable branching agents include phloroglucin, 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole, 4,6-dimethyl-2,4,6-tris (4-hy- droxyphenyl) hepten-2, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1, 3,5-tris (4-hydroxyphenyl) benzene, l, l, l-tris (4th -hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenylisopropyl)
• the polycarbonates can be prepared under the reaction conditions described in Stages with temperatures of 150 to 400 ° C are carried out, the dwell time in each stage can be 15 minutes to 5 hours, and the pressures are 1000 to 0.01 mbar.
• Additives are mold release agents, stabilizers, antioxidants, flame retardants, dyes and pigments, antistatic agents, nucleating agents, anti-dripping agents as well as organic and other inorganic fillers and reinforcing materials.
• Octadecanol 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide , 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.
• Suitable thiosynergists are, for example, dilauryl thiodipropionate and / or distearyl thiodipropionate.
• 2-hydroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2' -
• Salicylal-N'-salicyloyl hydrazine N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-l, 2,4 -triazole, bis- (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoylbisphenylhydrazide, N, N'-diacetyladipoyldihydrazide, N, N'-bis (salicyloyl) oxalyldihydrazide, N, N'-bis (salicyldihydidylzidylrazyl) Individual ones of these compounds or mixtures thereof can be used.
• Suitable impact modifiers are butadiene rubber with grafted-on styrene-acrylonitrile or methyl methacrylate, ethylene-propylene rubbers with grafted-on maleic anhydride, ethyl- and butyl-acrylate rubbers with grafted-on methyl methacrylate or styrene-acrylonitrile, interpenetrating methyl-acrylate-acrylate or acrylate-nitrate-methacrylate and acrylate-nitrate networks.
• Suitable colorants are pigments and organic and inorganic dyes.
• Comparative Examples 1, 2, 3 and 4 are linear polycarbonates and were prepared by a conventional interfacial polymerization process. They are sold by Bayer AG under the Makrolon ® 2808, 2408, KU1-1266 and 3108 brands.
• the polymers of Comparative Examples 5 and 6 are branched polycarbonates made by the interfacial polymerization process.
• Corresponding products are sold by Bayer AG under the Makrolon ® 1243 and 1239 brands. The relative viscosity was measured in a 0.5% solution of methylene chloride at 20 ° C.
• melt-polymerized polycarbonates contain multifunctional structural units, they show the same flow behavior characterized by the shear-thinning ratio as the interface-polymerized linear polycarbonates of the same relative viscosity.
• the polycarbonates also show surprisingly good color stability during injection molding.
• the branched polycarbonates 5 and 6 show a high degree of non-Newtonian flow behavior, which is typical for a branched polymer. Comparative Examples 5 and 6 contain 3,000 ppm of branching agent.

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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)
• Compositions Of Macromolecular Compounds (AREA)
• Polyesters Or Polycarbonates (AREA)

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• 2001
  • 2001-05-10 DE DE10122496A patent/DE10122496A1/de not_active Withdrawn
• 2002
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