DE19951729A1 - Polycarbonate blend compositions - Google Patents

Abstract

The disclosure relates to light scattering polymer compositions comprising polycarbonate which is mixed with polycycloolefins, for example, hydrogenated polystyrol, polystyrol copolymer and cycloolefin (co)polymers.

Description

The application relates to light-scattering polymer compositions which Include polycarbonate, which with polycycloolefins such as hydrogenated polystyrene, hydrogenated styrene polymers, hydrogenated cycloolefin (co) polymers, is mixed.

Light scattering polymers are often used as a material for lighting fixtures and Sun roofs, especially used for industrial buildings. These polymers scatter light more or less regularly in all directions. Also protect translucent roofs made of polycarbonate from sunshine radiation and avoid disadvantages for glass reinforced with metal wires are typical (difficult to cut) [DE-A-44 37 312, DE-A-22 51 708].

Light scattering materials are also used successfully in projection systems Procedure for hiding scratches and defects in rear projection screens, such as television screens or thin-film electronics decorative films (US 5,170,287).

Other possible applications for light-scattering polymers have been found at Leucht bodies, illuminated signs, especially opalisia illuminated from behind signs, skylights, motor vehicle sunroofs, covers for Automotive lights, etc. found.

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 ₃ are also used) or spherical particles based on poly (meth) acrylate have good opalescent properties .

Unfortunately, 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, there is no significant scatter and the material remains transparent (DE-A-20 19 325).

A decrease in the molecular weight of polycarbonate samples filled with inorganic fillers, in particular TiO ₂ , is another serious problem. Degradation has been observed to depend on the type and concentration of the filler. 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. The decrease in molecular weight could have a negative impact on the mechanical and other properties of the polymer. If 1.5% by weight of TiO _{2 is used} in a polycarbonate matrix, 0.15 to 0.2% by weight of water in polycarbonate is enough 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. In addition, 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).

Some of the disadvantages mentioned above (in particular matrix degradation, rough surface etc.) can be overcome by replacing inorganic scattering agents with organic particles consisting of different polymers. Some polyalkyl methacrylates and polyalkyl acrylates are widely used. The advantage of opalescent polycarbonates with organic light scattering agents is a five-fold reduction in the total concentration of additives. On the other hand, such systems show poor physical strength between the matrix and particles and poor dispersion; both result from the absence of strong adhesive forces between these two phases (US 5 237 004 and EP-A-269 324). Another disadvantage of particles based on polyalkyl methacrylate and polyalkyl acrylate for opalescent polycarbonates is 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.

To the above mentioned disadvantages rough, unevenly dispersed inorganic Avoiding particles becomes a low content according to the invention Polycycloolefin, preferably hydrogenated polycycloolefin, especially hydrogenated Polystyrene, used to introduce opal essence into polycarbonate. Such Hydrogenated polycycloolefins generate domains from one in the polycarbonate matrix separate phase that scatter light. The strong scattering effect of such polymer Domains in polycarbonate can be distinguished by a noticeable difference between the Refractive indexes of polycycloolefins and polycarbonate are explained.

The repeating units of preferred polycycloolefins shown in the invention such as hydrogenated polyvinylcyclohexane (HPS), Apel® and Arton® are in Scheme I shown. Hydrogenated polyvinylcyclohexane can be catalytic Hydrogenation of polystyrene can be synthesized (Examples 1 to 3), Arton® and Apel® are commercial products from Japan Synthetic Rubber or Mitsuff Corp.  

Scheme I

Usually, opalescent polycarbonates are made by compounding common polycarbonate with inorganic light-scattering compounds such as BaSO ₄ to produce a masterbatch that is further mixed with polycarbonate according to customer requirements. Using 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.

The opalescent polycarbonate blends and / or polycarbonate products according to the Invention are made by using hydrogenated polycycloolefins and Polycarbonates in common processes, preferably in a kneader or Extruder, mixed or compounded. For the production opalescent polycarbonate double wall sheets is preferably coextrusion used, preferably if UV protective layers (10 to 200 µm thick, preferably 60 microns thick), which cover the double-layer plates become.

Preferably up to 25 wt .-%, preferably 0.01 to 10 wt .-%, in particular 0.1 to 6 wt .-%, polycycloolefin incorporated into the polycarbonate.  

The basic properties of the blends according to the invention or of these blends manufactured product, such as haze and total transmission, are in Table I fathered. As can be seen from this table are small amounts of hydrogenated Polycycloolefins sufficient to disperse light almost completely To achieve polycarbonate compositions, the total transmission remains between 23 and 40% (for the wavelength range from 450 to 700 nm). The Relationship between turbidity and transmission can vary by varying the content light-scattering polymer additives can be easily fine-tuned. Polystyrene (PS) shows a significantly lower haze than its hydrogenated analogue.

On the other hand, the incorporation of the amounts of polycycloolefin did not deteriorate that mechanical properties of polycarbonate or polycarbonate products.

In addition to and in addition to HPS, Arton® and Apel®, other polycycloolefins can preferably also 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, polynorbornenes preferably prepared by polymerizing 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isopropyl-2-norbornene, 5-n-butyl- 2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-chloro-2-norbornene, 5-fluoro-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene 2-norbornene, bicyclo [2.2.1] hept-2-ene and its derivatives, tetracyclo [4.4.0.1 ^2.5 .1 ^7.10 ] -3-dodecene and its derivatives, hexacyclo [6.6.1.1 ^3.6 . 1 ^10.13 .0 ^2.7 .0 ^9.14 ] -4-heptadecene and its derivatives, octacyclo [8.8.0.1 ^2.9 .1 ^4.7 .1 ^11.18 .1 ^13.16 .0 ^{3, 8} .0 ^12.17 ] -5-docosen and its derivatives, pentacyclo [6.6.1.1 ^3.6 .0 ^2.7 .0 ^9.14 ] -4-hexadecene and its derivatives, Hepta-Cyclo [8.7.0. 1 ^2.9 .1 ^4.7 .1 ^11.17 .0 ^3.8 .0 ^12.16 ] -5-eicosen and its derivatives, Hepta cyclo [8.8.0.1 ^2.9 .1.1 ^4.7 .1 ^{11 , 17} .0 ^3.8 .0 ^12.16 ] -5-heneicosen and its derivatives, tri cyclo [4.3.0.1 ^2.5 ] -3-decene and its derivatives, tricyclo [4.4.0.1 ^2.5 ] -3 -undecene and its derivatives, pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] -4-pentadecene and its derivatives, pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^{9, 13} ] -4,10-pentadecadiene and its derivatives, heptacyclo- [8.7.0.1 ^3.6 .1 ^10.17 .1 ^12.15 .0 ^2.7 .0 ^11.16 ] -4-eicosen and its derivatives as well further ali cyclic monomers, as described in Canadian patent application 2 134 320 be.

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).

The following aromatic and aliphatic diols are recommended for such poly carbonates: 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-phenylenediisopropylidene) bisphenol, 4,4'-dihydroxybiphenyl, 4 , 4 '- (1,4-phenylene diisopropylidene) bisphenol, 4,4'-dihydroxydiphenyl sulfide, 1,1-bis (4-hydroxy phenyl) ethane, 4,4'-dihydroxydiphenyl, 2,4- (dihydroxyphenyl) -2 -methylbutane, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2 , 4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, α, α'-bis (3,5-dimethyl -4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2 , 2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4'-dihydroxy diphenyl sulfone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4 , 4'-dihydroxybenzophenone, 2,2 ', 6,6'-tetrabromo-2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) alkanes (1 to 25 carbon atoms in the alkane chain), 4.4 '-Dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, ethylene glycol bis (4-hydroxyphenyl) ether, 2,2-bis (4'-hydroxyphenyl) norbornane, 2,2-bis (4'-hydroxyphenyl ) adamantane, 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spiroindane, hydroquinone, resorcinol, hydrogenated bisphenol A, hydrogenated hydroquinone, hydrogenated resorcinol, 2,2,4,4 Tetramethyl-1,3-cyclobutanediol, m-dihydroxyxylylene, p-dihydroxycylylene, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [8.8] undecane, 2, 4'-dihydroxydiphenylsulfone, 2,2-bis (4-dihydroxy-3-methoxyphenyl) propane, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane, 1,4-cyclohexanedimethanol, 1,4-bis ( 2-hydroxyethoxy) -2-butyne, 4, 4 '- (9-fluorenylidene) bis (2-phenoxyethanol), trans-2,3-bis (4-hydroxyphenyl) -2-butene, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1, 1-dichloro-2,2-bis (4-hydroxyphenyl) ethylene, 1,1-dibromo-2,2-bis (4-hydroxyphenyl) ethylene, bis (4-hydroxyphenyl) sulfoxide, 2,7-dihydroxypyrene, 9 , 9-bis (4-hydroxyphenyl) fluorene, 2,7-dihydroxycarbazole, 2,6-dihydroxytrianthrene, phenolphthalein, indane bisphenol and their mixtures. Bisphenols containing five or six membered aliphatic rings and described in US Pat. No. 4,982,014 can also be used as comonomers. Bisphenol A and TMC-bisphenol (or their mixtures) are preferably used, most preferably bisphenol A. α, ω-dihydroxypolyolefins (e.g. Kraton Shell Liquid 2203, Kurraray TH-21® etc.), α, ω-dihydroxypolycarbonates , α, ω-dihydroxy polyesters, etc. Aromatic as well as aliphatic (or alicyclic) alcohols containing more than two hydroxy groups per molecule can be used as branching agents (and occasionally cross-linking agents). In addition to such a multifunctional alcohol, e.g. B. 1,4-bis (4 ', 4'-dihydroxytriphenyl methyl) benzene, nitrogen-containing agents can also be used, for. B. 3,3-bis (4-hydroxyphenol) -2-oxo-2,3-dihydroindole or isatin biscresol. In principle, chemical compounds which contain more than two alkyl or aryloxy carbonyl 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 conventional additives, such as white (titanium dioxide, preferably Kronos 2230) or other pigments (iron oxides, iron (III) hexa cyano-ferrate (II), chromium oxide etc.) and / or UV Stabilizers and / or anti-oxidants, such as sulfur-containing molecules such. B. Thioether-based compounds such. B. dilaurylthiodipropionate, distearylthiodipropionate, dimyristyl-3,3'-thiodipropionate, pentaerythritol tetrakis (β-laurylthiopropionate), phosphites (phenyldiisodecyl phosphite, phenylisodecylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite (tris (nonylphenyl) cyclos tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4'-diisopropylidenediphenolalkyl (C ₁₂ -C ₁₅ ) 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) etc.), hindered phenols 1 , 1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 4,4'-butylidenebis (3-methyl-t-butylphenol), n-octadecyl-3- (3 ', 5th '-di-t-butyl-4'-hydroxyphenyl) propionate, 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 (4-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, 4,4-thiobis (3-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris ( 3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,2-thiodiethylenebis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane etc.), hydrophosphites, Phosphonites and / or diphosphonites such as tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphonite, etc.

The following examples will illustrate the invention. The invention is not based on limited the examples.  

Examples example 1 Preparation of the polystyrene solution in cyclohexane

117.82 kg of distilled cyclohexane are placed under nitrogen in a 500 l stirred kettle transferred and heated to 50 ° C. Then 48.29 kg will be within 4 hours Polystyrene (PS) added to the solution with stirring. The solution is omitted Stir for another 24 hours at 70 ° C. After cooling, 53.32 kg of MTBE (Methyl tert-butyl ether) at 50 ° C under nitrogen in the stirred mixture. The stirred solution is then cooled to room temperature.

Example 2 Hydrogenation of polystyrene using a Ni catalyst

A 40 l autoclave equipped with a stirrer becomes 21.943 kg Polystyrene solution (21.943 kg solution = 4.829 kg PS + 11.782 kg cyclohexane + 5.332 kg MTBE), and then 625 g Ni catalyst in 2.95 l MTBE added. The autoclave is stirred, the corresponding hydrogen pressure becomes set to 100 bar and the reactor is heated to 160 ° C. with stirring. The Pressure is automatically kept constant at 100 bar during the reaction. The The reaction is stopped when no more hydrogen is consumed and then the reaction mixture is stirred for 2 to 4 hours. After removing the Filtration of the hydrogenated polymer by evaporation of the catalyst Solvent isolated.

Example 3 Mixing HPS with polycarbonate in a kneader

A twin screw kneader Haake Rheomix 600 in connection with the Processing unit Haake Reocord 90 is heated to 290 ° C, with 95 g Polycarbonate and 5 g of polyvinylcyclohexane filled, taking the dosing unit Katron Soder T-20 used under a stream of nitrogen and it will take an 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 Polycarbonate (Makrolon 1243) and 5 g of polyvinylcyclohexane filled, whereby the Dosing unit Katron-Soder T-20 used. That through a nozzle with a round Melted blend is guided with a conveyor belt and a cross section Cooling trough (both Brabender OHG) to a granulation unit (CF-Scheer & Cie) transported.

Example 5

Turbidity and transmission experiments are performed using plates measured from 60 mm × 60 mm × 2 mm. A HazeGard turbidimeter (BYK-Gardner) is used for turbidity experiments according to ASTM-1003/290.

Transmission spectra are generated using a Perkin-Elmer Lambda 900 photometers equipped with a spherical detector are recorded, using air as a reference. The turbidity and total transmissions experiments are summarized in Table I.  

Table I

Haze and overall transmission for polycarbonates containing a polymeric light scattering agent.

Example 6

Stress-strain experiments are carried out at room temperature with the fret bars No. 3 (170 mm × 10 mm × 4 mm) performed using an Instron 5566 at a speed of 5 mm / min. Shock tests are carried out with bars from 80 mm × 10 mm × 4 mm. Samples with a 2 mm V notch are used for used a notched impact test. The mechanical properties of PC with 1% and 5% HPS are summarized in Table II.  

Table II

Mechanical properties of polycarbonate mixed with HPS (Makrolon 1243)

Example 7 Extrusion double wall sheets

A granulate of an HPS-polycarbonate blend which contains 3% by weight of HPS is prepared according to Example 5 and then in a special extruder S-70 (Bayer AG) Double wall sheets (each layer 1 mm thick) with a 60 µm thick UV Protective layer (Bayer AG-DP1-1244 / 5-55 / 0.54) coextruded. The Rotationsge speed 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 260 ° C and in zones 4 to 6 and in the exit 250 ° C.

Example 8

Mechanical properties of the double-wall sheets produced according to Example 7 are estimated using a hail test according to DIN 53 443. One piece Double-wall sheets (formed according to Example 6), 50 mm wide and 350 mm long, is from a height of 20 mm from a spherical mandrel with a diameter of 5 mm hit. The mandrel is loaded with a weight of 36 kg. The experiment is carried out at 23 ° C. The results of the test are shown in Table III.  

Table III

Destructive strength Fs, destructive elongation Ls and destructive energy Ws, determined in the hail test on a double-layer polycarbonate plate (one layer = 1 mm), which contained 3% by weight HPS.

Example 9 Direct extrusion double wall sheets made of polycarbonate and HPS

Polycarbonate and HPS (weight ratio 97: 3) are without prior Compounding in a special extruder S-70 (Bayer AG) as a double-layer plate (each layer 1 mm thick) with a 60 µm thick UV protective layer (Bayer AG-DP1-1244 / 5-55 / 054) 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 260 ° C and in the zones 4 to 6 and in the outlet 250 ° C.

Claims (10)

1. Polymer compositions which ver with cycloolefin (co) polymers include mixed polycarbonate. 2. Polymer compositions according to claim 1, which up to 25 wt .-% Cycloolefin (co) polymers. 3. Polymer compositions according to claim 1 and / or 2, the hydrogenated Polystyrene or hydrogenated polystyrene copolymers. 4. Polymer compositions of any of the preceding claims, comprising a polycarbonate at 300 ° C a melt volume flow rate of 3-8 cm ^3/10 min has mutandis. 5. Polycarbonate blends comprising cycloolefin (co) polymers. 6. Polycarbonate products or materials that contain polycarbonate Cycloolefin (co) polymers include. 7. Use cycloolefin (co) polymers as light scattering agents in poly carbonates. 8. Use of polymer compositions according to claim 1 for Manufacture of light-diffusing products or materials. 9. Use of polycarbonate blends according to claim 2 for the production light-diffusing products or materials. 10. Process for the preparation of light-scattering polymer compositions Mixing polycarbonate with cycloolefin (co) polymers.