EP1238012A1 - Compositions de melanges de polycarbonate - Google Patents

Compositions de melanges de polycarbonate

Info

Publication number
EP1238012A1
EP1238012A1 EP00972767A EP00972767A EP1238012A1 EP 1238012 A1 EP1238012 A1 EP 1238012A1 EP 00972767 A EP00972767 A EP 00972767A EP 00972767 A EP00972767 A EP 00972767A EP 1238012 A1 EP1238012 A1 EP 1238012A1
Authority
EP
European Patent Office
Prior art keywords
polycarbonate
bis
hydroxyphenyl
polymers
light
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Withdrawn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
EP00972767A
Other languages
German (de)
English (en)
Inventor
Miroslav Marek
Volker Wege
Friedrich-Karl Bruder
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.)
Bayer AG
Original Assignee
Bayer 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 AG filed Critical Bayer AG
Publication of EP1238012A1 publication Critical patent/EP1238012A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/10—Homopolymers or copolymers according to C08L39/00 - C08L49/00; Derivatives thereof

Definitions

  • the application relates to light-scattering polymer compositions comprising polycarbonate mixed with polycycloolefins, such as hydrogenated polystyrene, hydrogenated styrene polymers, hydrogenated cycloolefin (co) polymers.
  • polycycloolefins such as hydrogenated polystyrene, hydrogenated styrene polymers, hydrogenated cycloolefin (co) polymers.
  • Light-scattering polymers are often used as a material for lighting fixtures and sunroofs, especially for industrial buildings. These polymers scatter light more or less regularly in all directions.
  • translucent roofs made of polycarbonate protect against sunlight and avoid disadvantages that are typical for glass reinforced with metal wires (difficult to cut) [DE-A-44 37 312, DE-A-22 51 708].
  • Light scattering in originally transparent polycarbonates is achieved by adding scattering agents to the polymer.
  • Polycarbonates filled with inorganic additives or pigments particles of BaSO 4 and TiO 2 are mostly used for this purpose, but ZnO, ZnS, CdS, CaCO are also used) or spherical particles based on poly (meth) acrylate have good opalescent properties.
  • these systems may experience problems related to the relationship between transparency and opacity, mechanical properties, and stability.
  • White pigments, such as TiO 2, ZnO, ZnS reduce light transmission so much that it limits their application as a brightening material. If the pigment concentration decreases, no significant occurs
  • a further serious problem is a decrease in the molecular weight of polycarbonate samples filled with inorganic fillers, in particular TiO 2. It has been observed that the degradation is of the type and concentration of the
  • Inorganic pigments are presumably involved in such degradation reactions that take place during processing (e.g. injection molding), especially if traces of water (e.g. as air humidity) are present in the polymer.
  • traces of water e.g. as air humidity
  • the decrease in molecular weight could have a negative impact on the mechanical and other properties of the polymer. If 1.5% by weight
  • TiÜ2 are used in a polycarbonate matrix, 0.15 to 0.2% by weight of water in polycarbonate is sufficient to cause the matrix to degrade (DE-A-20 19 325).
  • Inorganic particles are difficult to distribute evenly throughout the matrix, and because they are hard and irregularly ground, they tend to grind down the processing equipment.
  • polycarbonate articles containing such particles have an irregular surface. Dimples and holes caused by large BaSO 4 particles can be observed (EP-A-269 324 and EP-A-634 446).
  • Polyalkylacrylate base for opalescent polycarbonates consists in the need to use a certain amount of TiO 2 so that they actually do not completely avoid the use of the problematic inorganic pigments.
  • the thermal stability of the polyalkyl (meth) acrylate particles is low, their use in the lighting fixture is very limited.
  • a low content of polycycloolefin preferably hydrogenated polycycloolefin, in particular hydrogenated polystyrene, is used to introduce opal essence into polycarbonate.
  • polycycloolefins preferably hydrogenated polycycloolefin, in particular hydrogenated polystyrene
  • Such hydrogenated polycycloolefins produce domains in the polycarbonate matrix from a separate phase that scatter light.
  • the strong scattering effect of such polymeric domains in polycarbonate can be explained by a noticeable difference between the refractive indices of the polycycloolefins and the polycarbonate.
  • the repeating units of preferred polycycloolefins shown in the invention such as hydrogenated polyvinylcyclohexane (HPS), Apel® and Arton®, are shown in Scheme I.
  • Hydrogenated polyvinylcyclohexane can be synthesized by catalytic hydrogenation of polystyrene (Examples 1 to 3), Arton® and Apel® are commercial products from Japan Synthetic Rubber and Mitsui Corp.
  • opalescent polycarbonates are made by compounding ordinary polycarbonate with inorganic light-scattering compounds such as BaSO 4 to produce a masterbatch that is further blended with polycarbonate according to customer requirements.
  • inorganic light-scattering compounds such as BaSO 4
  • polymeric light scattering agents it is possible according to the invention to produce the end product in one step without using a prepared polycarbonate blend (master batch), so that the production costs are reduced.
  • Invention are produced by mixing or compounding hydrogenated polycycloolefins and polycarbonates in common processes, preferably in a kneader or extruder. Coextrusion is preferably used for the production of opalescent polycarbonate double-wall sheets, preferably if UV protective layers (10 to 200 ⁇ m thick, preferably 60 ⁇ m thick) covering the double-layer sheets are produced.
  • polycycloolefin Up to 25% by weight, preferably 0.01 to 10% by weight, in particular 0.1 to 6% by weight, of polycycloolefin are preferably incorporated into the polycarbonate.
  • the total transmission remains between 23 and 40% (for the wavelength range from 450 to 700 nm).
  • the relationship between haze and transmission can be easily fine-tuned by varying the level of light-scattering polymer additives.
  • Polystyrene (PS) shows a significantly lower haze than its hydrogenated analogue.
  • Polycycloolefins can be used to induce a light-scattering effect in polycarbonates, such as: polycyclobutene, polycyclopentene, polycyclohexene, 3, 4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1 -cyclohexene, cyclooctene, polynorbornene (preferably prepared by polymerizing 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isopropyl-2-norbornene,
  • Pentacyclo [6.5.1.1 3 '6 .0 2' 7 .0 9 '13] -4,10-pentadecadiene and its derivatives, Heptacyclo- [8.7.0.1 3 '.l 6 10' 17 .l 12 '15 .0 2' 7 .0 11> 16] -4-eicosene and its derivatives as well as other ali- cyclic monomers as described in Canadian patent application 2 134 320 are described.
  • Polycarbonates which are used for the described mixing or compounding with light-scattering polymeric agents can be prepared either by a phosgenation process or by melt polymerization.
  • Preferred polycarbonates have a melt volume flow rate (ISO 1133, 300 ° C., 10 min) of 3 to 8 cm 3 / (10 min), preferably 6 cm 3 / (10 min).
  • aromatic and aliphatic diols are recommended for such polycarbonates: 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxyphenyl) perfluoropropane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1, 1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane (TMC-bisphenol), 4,4 '- (1,3-phenylene-di-isopropylidene) bisphenol, 4,4'-dihydroxybiphenyl, 4 , 4 '- (1,4-phenylenediisopropylidene) bisphenol, 4,4'-dihydroxydiphenyl sulfide, 1,1-bis (4-hydroxyphenyl) ethane, 4,4'-dihydroxydiphenyl, 2,4- (dihydroxyphenyl) -2-methylbutane, ⁇ , ⁇ '-bis (4-hydroxyphenyl) -p-d
  • branching agents e.g. 1,4-bis (4 ', 4'-dihydroxytriphenylmethyl) benzene
  • nitrogen-containing agents can also be used, e.g. 3,3- bis (4-hydroxyphenol) -2-oxo-2,3-dihydroindole or isatin biscresol.
  • chemical compounds which contain more than two alkyl or aryloxycarbonyl groups can be used for branching (crosslinking can take place in concentrations higher than 1 mol%).
  • the resulting translucent polycarbonate blends according to the invention can additionally contain 10 to 5000 ppm of customary additives, such as white (titanium dioxide, preferably Kronos 2230) or other pigments (iron oxides, iron (III) hexacyano ferrate (II), chromium oxide etc.) and / or UV stabilizers and / or antioxidants, such as sulfur-containing molecules (e.g.
  • thioether such as dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl 3,3'-thiodi- propionate, pentaerythritol tetrakis (.beta.-laurylthiopropionate), phosphites (Phenyldiisodecyl- phosphite, Phenylisodecylphosphit, triphenyl phosphite, tris (nonylphenyl) phosphite, tricyclohexyl phosphite, tricresyl phosphite, tris (2,4- di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol dip
  • Pentaerythrityl tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), triethylene glycol bis (3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate, 1,6-hexanediol -bis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4th -ethyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl ) -4-methylphenyl acrylate, 2- (1- (2-hydroxy-3,5-di-t-butylphenyl) ethyl) -4,6-dineopentylphenyl acrylate,
  • a twin screw kneader Haake Rheomix 600 in conjunction with the processing unit Haake Reocord 90 is heated to 290 ° C, filled with 95 g polycarbonate and 5 g polyvinylcyclohexane, using the dosing unit Katron-Soder T-20 under a nitrogen stream and it becomes one hour long kneaded (40 rpm).
  • Example 4 Mixing HPS with polycarbonate in an extruder
  • a twin screw extruder Haake Rheomix TW 100 in connection with the processing unit Haake Rheocord 90 is heated to 300 ° C with 95 g
  • Turbidity and transmission experiments are measured using 60 mm x 60 mm x 2 mm plates.
  • a granulate of an HPS-polycarbonate blend which contains 3% by weight of HPS is produced according to Example 5 and then in a special extruder S-70 (Bayer AG) as double-wall sheets (each layer 1 mm thick) with a 60 ⁇ m thick UV - Protective layer (Bayer AG - DPI - 1244 / 5-55 / 0.54) coextruded.
  • the speed of rotation is 38 rpm
  • the temperature in the feed zone is 270 ° C, in the first zone 280 ° C, in the second zone 270 ° C, in the third zone
  • A tough-brittle
  • B smooth break

Landscapes

  • 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)
  • Optical Elements Other Than Lenses (AREA)

Abstract

L'invention concerne des compositions de mélanges de polycarbonate, qui comprennent du polycarbonate, mélangé à des polycyclo-oléfines, telles que du polystyrène hydrogéné, un copolymère polystyrène et des (co)polymères cyclo-oléfine.
EP00972767A 1999-10-27 2000-10-16 Compositions de melanges de polycarbonate Withdrawn EP1238012A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19951729 1999-10-27
DE19951729A DE19951729A1 (de) 1999-10-27 1999-10-27 Polycarbonatblendzusammensetzungen
PCT/EP2000/010142 WO2001030909A1 (fr) 1999-10-27 2000-10-16 Compositions de melanges de polycarbonate

Publications (1)

Publication Number Publication Date
EP1238012A1 true EP1238012A1 (fr) 2002-09-11

Family

ID=7927043

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00972767A Withdrawn EP1238012A1 (fr) 1999-10-27 2000-10-16 Compositions de melanges de polycarbonate

Country Status (7)

Country Link
EP (1) EP1238012A1 (fr)
JP (1) JP2003513134A (fr)
KR (1) KR20020047281A (fr)
CN (1) CN1382188A (fr)
AU (1) AU1138501A (fr)
DE (1) DE19951729A1 (fr)
WO (1) WO2001030909A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10152146A1 (de) * 2001-10-25 2003-05-22 Ticona Gmbh Verfahren zur Reduzierung der Zähigkeit mechanisch zu bearbeitender Formteile aus Kunststoff sowie deren Verwendung
KR100574092B1 (ko) * 2003-08-27 2006-04-27 제일모직주식회사 광확산성을 갖는 열가소성 수지 조성물
JP5063873B2 (ja) * 2005-07-05 2012-10-31 出光興産株式会社 光拡散性ポリカーボネート系樹脂組成物、および同樹脂組成物を用いた光拡散板
JP5334779B2 (ja) * 2009-09-29 2013-11-06 ユニチカ株式会社 樹脂組成物及び該樹脂組成物からなる成形体
CN103554882A (zh) * 2013-10-26 2014-02-05 安徽省富光实业股份有限公司 一种水杯壳体用改性聚碳酸酯材料及其制备方法
CN103525065A (zh) * 2013-10-26 2014-01-22 安徽省富光实业股份有限公司 一种用于制作水杯壳体的聚碳酸酯组合材料及其制备方法
CN116622207B (zh) * 2023-05-27 2023-10-27 东莞市华驰高分子材料有限公司 一种屏幕用保护膜及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3300855A1 (de) * 1982-01-29 1983-08-11 General Electric Co., Schenectady, N.Y. Thermoplastische formmasse
JPS59179661A (ja) * 1983-03-31 1984-10-12 Bando Chem Ind Ltd 含油合成樹脂組成物
EP0647676B1 (fr) * 1993-10-06 1999-07-21 Ticona GmbH Copolymère de cyclo-oléfine modifié
JPH10130486A (ja) * 1996-10-30 1998-05-19 Arakawa Chem Ind Co Ltd ポリカーボネート系樹脂用改質剤およびポリカーボネート系樹脂組成物
DE19756368A1 (de) * 1997-12-18 1999-07-01 Bayer Ag Vinylcyclohexan basierende Polymere

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0130909A1 *

Also Published As

Publication number Publication date
JP2003513134A (ja) 2003-04-08
DE19951729A1 (de) 2001-05-03
KR20020047281A (ko) 2002-06-21
CN1382188A (zh) 2002-11-27
AU1138501A (en) 2001-05-08
WO2001030909A1 (fr) 2001-05-03

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