CN1382188A - Blended polycarbonate compositions - Google Patents

Blended polycarbonate compositions Download PDF

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Publication number
CN1382188A
CN1382188A CN00814756A CN00814756A CN1382188A CN 1382188 A CN1382188 A CN 1382188A CN 00814756 A CN00814756 A CN 00814756A CN 00814756 A CN00814756 A CN 00814756A CN 1382188 A CN1382188 A CN 1382188A
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polycarbonate
cycloolefin
hydroxyphenyl
total
polymer composition
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M·马雷克
V·维格
F·K·布鲁德
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Bayer AG
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Bayer AG
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    • 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

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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)
  • Optical Elements Other Than Lenses (AREA)

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 polycarbonate compositions of blend
The application relates to the light diffusion polymer composition, and it comprises the polycarbonate with following poly-cycloolefin blend: as hydrogenated polystyrene, hydrogenated styrene polymer, hydrogenation cycloolefin (being total to) polymkeric substance.
The light diffusion polymkeric substance as the material of lighting fitting and sun proof, is used in particular for industrial building usually.These polymkeric substance are more regular or diffused light more brokenly on all directions.The translucent roof of being made by polycarbonate provides the protection of incident sunlight and avoids typically being the shortcoming (being difficult to cutting) [DE-A-44 37 312, and DE-A-22 51708] of reinforcing glass in addition.
The light diffusion material also is successfully used to optical projection system, as hiding back projection screen, as the method (US 5 170 287) of scratch in TV screen or the thin layer electronics decorating film and defective.
May using in addition of light diffusion polymkeric substance found in following application: lighting fitting, be subjected to according to mark, be used in particular for counter being subjected to according to opalescence mark, up ligthing device, automobile sunshade awning top, automobile lampshade etc.
By in polymkeric substance, adding light diffusing agent, reach the light diffusion in originally transparent polycarbonate.With inorganic additives or pigment (BaSO 4And TiO 2Particle be generally used for this purpose, but also use ZnO, ZnS, CdS, CaCO 3), or the polycarbonate of filling based on the spheroidal particle of poly-(methyl) acrylate shows good opalescence performance.
Lamentedly, in these systems, may appearance and transparency and optical haze degree between, relevant problem between mechanical property and the stability.White pigment is as TiO 2, ZnO, ZnS have seriously reduced light transmission, make them limit its range of application as an illuminating material.If pigment concentration descends, significant diffusion and material do not take place keep transparent (DE-A-20 19325).
With mineral filler, TiO particularly 2The molecular weight of the polycarbonate material of filling reduces, and is another serious problem.Type and concentration that such degraded depends on filler have been observed.The such DeR of the general participation of mineral dye, DeR takes place during processing (for example injection moulding), if particularly there is water (for example as atmospheric water) in polymkeric substance.The reduction meeting of molecular weight has a negative impact to machinery and other performance of polymkeric substance.If in polycarbonate matrix, use the TiO of 1.5wt% 2, the water-content of 0.15-0.2wt% is enough to cause the degraded (DE-A-20 19 325) of matrix in the polycarbonate.
Because they are hard and be irregular grinding, inorganic particulate is difficult to uniform distribution in matrix, and they tend to cause the wearing and tearing of processing units.In addition, the polycarbonate article that comprises this like-particles has irregular surface.Can observe pit and hole, they are by big BaSO 4Particle causes (EP-A-269 324 and EP-A-634 446).
By replacing inorganic light diffuser, can overcome some above-mentioned shortcomings (particularly matrix degraded, uneven surface etc.) with the organic filler of forming by other polymkeric substance.Usually use some polyalkyl methacrylate and polyalkyl acrylate.The advantage that comprises the opalescence polycarbonate of organic light scattering agent is that the additive total concn reduces by five times.On the other hand, such system is presented at physical strength relatively poor between matrix and the particle and relatively poor dispersion, and the two is owing to lack strong bounding force (US 5 237 004 and EP-A-269 324) between this two-phase.Be used for the opalescence polycarbonate, be to use a certain amount of TiO based on another shortcoming of the particle of polyalkyl methacrylate and polyalkyl acrylate 2, the feasible use that in fact can not avoid the problem mineral dye fully.Poly-(methyl) alkyl acrylate has low thermostability and its purposes in lighting fitting is severely limited.
For avoiding coarse, the above-mentioned shortcoming of irregular dispersive inorganic particulate, the poly-cycloolefin of lower aq used according to the invention, preferred hydrogenation poly-cycloolefin, particularly hydrogenated polystyrene are given the polycarbonate opalescence.The poly-cycloolefin of such hydrogenation produces the microcell that separates phase, these microcell diffused lights in polycarbonate matrix.The strong diffusion effect of these polymer domains in the polycarbonate, but can explain by the difference in perception between poly-cycloolefin specific refractory power and polycarbonate specific refractory power.
Structural formula I shows the preferred poly-cycloolefin that shows in the present invention, as hydrogenation polyvinyl eyclohexane (HPS), Apel And Arton Repeating unit.The hydrogenation polyvinyl eyclohexane can be by the catalytic hydrogenation synthetic (embodiment 1-3) of polystyrene, Arton And Apel It is respectively the commercially available prod of JapanSynthetic Rubber and Mitsui Corp..
Structural formula I
The opalescence polycarbonate is produced by following mode usually: with standard polycarbonate and inorganic, the light diffusion compound is as BaSO 4Mixing, to produce masterbatch, according to requirement of client, it further mixes with polycarbonate.Use the polymkeric substance light diffusing agent, can in one step, produce final product according to the present invention, and not need to use previously prepared polycarbonate Alloys (masterbatch), reduced production cost like this.
According to opalescence polycarbonate Alloys of the present invention and/or polycarbonate products is in common technology, preferably in kneading machine or forcing machine, by mixing or the poly-cycloolefin of mixing hydrogenation and polycarbonate production.Preferred if production covers the UV protective layer (10-200 μ m is thick, and preferred 60 μ m are thick) of double layer sheet, opalescence polycarbonate twin wall sheet material is preferably by coextrusion production.
Preferably, incite somebody to action 25wt% at the most, the poly-cycloolefin of preferred 0.01-10wt%, particularly 0.1-6wt% is incorporated in the polycarbonate.
The fundamental property of the product of producing according to blend of the present invention or by these blends as optical haze degree and total transmittance, sees Table I.As seen in can from then on showing, the poly-cycloolefin of a spot of hydrogenation is enough to reach light diffusion in fact completely in the polycarbonate compositions, and wherein total transmittance remains 23-40% (for the wavelength region of 450-700nm).By changing the content of light diffusion polymeric additive, can easily meticulous adjusting optical haze degree and transmissivity between relation.Compare with its hydrogenated analogs, polystyrene (PS) shows the lower optical haze degree of essence.
In addition, the poly-cycloolefin of introducing this tittle does not damage the mechanical property of polycarbonate or polycarbonate products.
Remove HPS, Arton And Apel In addition, also can preferably use following other poly-cycloolefin, in polycarbonate, to produce the light diffusion effect: as poly-cyclobutene, poly-cyclopentenes, poly-tetrahydrobenzene, 3, the 4-dimethylcyclopentene, the 3-tetrahydrotoluene, 2-(2-methyl butyl)-1-tetrahydrobenzene, cyclooctene, polynorbornene is (preferably by the following material production of polymerization: the 2-norbornylene, 5-methyl-2-norbornylene, 5-ethyl-2-norbornylene, 5-sec.-propyl-2-norbornylene, 5-normal-butyl-2-norbornylene, 5-isobutyl--2-norbornylene, 5,6-dimethyl-2-norbornylene, 5-chloro-2-norbornylene, 5-fluoro-2-norbornylene, 5-vinyl-2-norbornylene, 5-ethylidene-2-norbornene, dicyclo [2.2.1]-2-heptene and derivative thereof, Fourth Ring [4.4.0.1 2.5.1 7.10]-3-dodecylene and derivative thereof, six ring [6.6.1.1 3.6.1 10.13.0 2.7.0 9.14]-4-heptadecene and derivative thereof, eight ring [8.8.0.1 2.9.1 4.7.1 11.18.1 11.36.0 3.8.0 12.17]-5-two dodecylenes and derivative thereof, five rings [6.6.1.1 3.6.0 2.7.0 9.14]-4-cetene and derivative thereof, seven ring [8.7.0.1 2.9.1 4.7.1 11.17.0 3.8.0 12.16]-5-eicosylene and derivative thereof, seven ring [8.8.0.1 2.9.1 4.7.1 11.17.0 3.8.0 12.16]-5-heneicosene and derivative thereof, three ring [4.3.0.1 2.5]-3-decene and derivative thereof, three ring [4.4.0.1 2.5]-3-undecylene and derivative thereof, five rings [6.5.1.1 3.6.0 2.7.0 9.13]-4-15 carbenes and derivative thereof, five rings [6.5.1.1 3.6.0 2.7.0 9.13]-4,10-15 carbon diene and derivative thereof, seven ring [8.7.0.1 3.6.1 10.17.1 12.15.0 2.7.0 11.16]-4-eicosylene and derivative thereof and other alicyclic monomer, those as in Canadian patent application 2 134 320, describing.
Be used for and blend of light diffusion polymer agent or mixing polycarbonate, can be by carbonyl chloride technology or by melt polymerization production.(1133,300 ℃ of ISO 10min) are 3-8cm to the melt volume-flow rate of preferred polycarbonate 3/ (10min), preferred 6cm 3/ (10min).
Recommend following aromatics and aliphatic diol to be used for such polycarbonate: 2, two (4-hydroxyphenyl) propane (dihydroxyphenyl propane) of 2-, 2, two (4-hydroxyphenyl) perfluoropropane of 2-, 1, two (4-hydroxyphenyl) hexanaphthenes of 1-, 1, two (the 4-hydroxyphenyl)-3 of 1-, 5,5-trimethyl-cyclohexane (TMC bis-phenol), 4,4 '-(1,3-phenylene two isopropylidenes) bis-phenol, 4,4 '-dihydroxybiphenyl, 4,4 '-(1,4-phenylene two isopropylidenes) bis-phenol, 4,4 '-dihydroxyl diphenyl sulfide, 1, two (4-hydroxyphenyl) ethane of 1-, 4,4 '-dihydroxyl phenylbenzene, 2,4-(dihydroxyphenyl)-2-methylbutane, α, α '-two (4-hydroxyphenyl)-right-diisopropylbenzene(DIPB), 2, two (3-methyl-4-hydroxyphenyl) propane of 2-, 2, two (the 3-chloro-4-hydroxyphenyl) propane of 2-, two (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-two (3,5-dimethyl-4-hydroxyphenyl) propane, two (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-two (3,5-dimethyl-4-hydroxyphenyl)-the 2-methylbutane, 1,1-(3,5-dimethyl-4-hydroxyphenyl) hexanaphthene, α, α '-two (3,5-dimethyl-4-hydroxyphenyl)-right-diisopropylbenzene(DIPB), 2,2-two (3,5-two chloro-4-hydroxyphenyl) propane, 2,2-two (3,5-two bromo-4-hydroxyphenyl) propane, 4,4 '-dihydroxy-diphenyl sulfone, 2, the 6-dihydroxy naphthlene, 2, the 7-dihydroxy naphthlene, 1, the 5-dihydroxy naphthlene, 1, the 6-dihydroxy naphthlene, 4,4 '-dihydroxy benzophenone, 2,2 ' 6,6 '-tetrabromobisphenol, two (4-hydroxyphenyl) propane of 2-, two (4-hydroxyphenyl) alkane (1-25 carbon atom arranged on alkane chain), 4,4 '-dihydroxy diphenyl ether, 4,4 '-dihydroxyl-3,3 '-dimethyl phenyl ether, ethylene glycol bis (4-hydroxyphenyl) ether, 2, two (4 '-hydroxyphenyl) norbornanes of 2-, 2, two (4 '-hydroxyphenyl) diamantane of 2-, 6,6 '-dihydroxyl-3,3,3 ', 3 '-tetramethyl--1,1 '-spiral shell indane, Resorcinol, Resorcinol, Hydrogenated Bisphenol A, the hydrogenation Resorcinol, hydroresorcinol, 2,2,4,4-tetramethyl--1,3-tetramethylene glycol, between-dihydroxyl-dimethylbenzene, right-dihydroxyl-dimethylbenzene, 3, two (the 2-hydroxyls-1 of 9-, the 1-dimethyl ethyl)-2,4,8,10-Si Evil spiral shell [8.8] undecane, 2,4 '-dihydroxy-diphenyl sulfone, 2, two (4-dihydroxyl-3-p-methoxy-phenyl) propane of 2-, two (methylol) three ring [5.2.1.0 2.6] decane, 1,4-cyclohexanedimethanol, 1, two (2-the hydroxyl-oxethyl)-2-butyne, 4 of 4-, 4 '-(9-fluorenylidene)-two (2-phenoxyethyl alcohols), trans-2, two (4-the hydroxyphenyl)-2-butylene, 2 of 3-, two (3-cyclohexyl-4-hydroxyphenyl) propane, 1 of 2-, 1-two chloro-2, two (4-hydroxyphenyl) ethene, 1 of 2-, 1-two bromo-2, two (4-hydroxyphenyl) ethene of 2-, two (4-hydroxyphenyl) sulfoxide, 2,7-dihydroxyl pyrene, 9, two (4-hydroxyphenyl) fluorenes, 2 of 9-, 7-dihydroxyl carbazole, 2,6-dihydroxyl three anthrenes, phenolphthalein, indane bis-phenol and composition thereof.Also can use such bis-phenol as comonomer, they comprise five yuan or hexa-atomic aliphatic series ring and are described in the US patent 4 982 014.Preferred dihydroxyphenyl propane and TMC bis-phenol (or its mixture), the most preferably dihydroxyphenyl propane of using.α, (for example KratonShell Liquid 2203, Kuraray TH-21 for the alpha, omega-dihydroxy polyolefine Deng), α, the alpha, omega-dihydroxy polycarbonate, α, alpha, omega-dihydroxy polyester etc., aromatics and aliphatic series (or alicyclic) alcohol comprises in their each molecules more than two hydroxyls, can be used as branching agent (with occasionally as linking agent).Remove such polyfunctional alcohol, for example 1, beyond two (4 ', the 4 '-dihydroxyl trityl group) benzene of 4-, also can use nitrogenous reagent, for example 3, two (4-the hydroxyl phenol)-2-oxos-2 of 3-, the two cresols of 3-indoline or isatin.In principle, also can use the compound that comprises more than two alkyl or aryloxycarbonyl, to reach branching (crosslinked can be higher than under the concentration of 1mol% take place).
The translucent polycarbonate Alloys of the present invention that obtains, the conventional additives that can comprise 10-5000ppm in addition, as white pigment (titanium dioxide, preferred Kronos 2230), and/or other pigment (ferric oxide, iron (III) six cyano group ferrates (II), chromic oxide etc.), and/or UV stablizer and/or oxidation inhibitor, as comprise molecule (the thioether group compound for example of sulphur, as the two dodecyl esters of thio-2 acid, the distearyl thiodipropionate, 3,3 '-thio-2 acid, two myristins, four (β-dodecyl propane thioic acid) pentaerythritol ester, phosphorous acid ester (phosphorous acid phenyl two isodecyl esters, phosphorous acid phenyl isodecyl ester, triphenyl phosphite, tricresyl phosphite (nonyl benzene) ester, the tricresyl phosphite cyclohexyl, tricresyl phosphite, tricresyl phosphite (2,4-two-tert.-butylbenzene) ester, tricresyl phosphite (nonyl benzene) ester, two (2,4-two-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-two-tertiary butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, 2,2-methylene-bis (4,6-two-tert-butyl-phenyl) octyl group phosphorous acid ester, 4,4 '-two isopropylidene biphenol alkyl (C 12-C 15), 4,4 '-butylidene two (the two three decyl phosphorous acid esters of 3-methyl-6-tert butyl phenyl) etc.), hindered phenol (1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 4,4 '-butylidene two (3-methyl-tert.-butyl phenol), Octadecane base-3-(3 ', 5 '-two-tertiary butyl-4 '-hydroxyphenyl) propionic ester, (3-(3 for tetramethylolmethane four, 5-two-tertiary butyl-4-hydroxyphenyl) propionic ester, two (3-(the 3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionic esters of triglycol, 1, the 6-hexylene glycol is two, and (3-(3,5-two-tertiary butyl-4-hydroxyphenyl) propionic ester, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate, 2-(1-(2-hydroxyl-3,5-two-tert-butyl-phenyl) ethyl)-4,6-di neo-pentyl phenyl acrylate, 4,4-thiobis (3 methy 6 tert butyl phenol), 1,3,5-trimethylammonium-2,4,6-three (3,5-two-tertiary butyl-4-hydroxyphenyl) benzene, 2, (3-(3 for 2-sulfo-di ethylene bis, 5-two-tertiary butyl-4-hydroxyphenyl) propionic ester, 3, two (the 2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1 of 9-, the 1-dimethyl)-2,4,8,10-Si Evil spiral shell [5.5] undecane etc.), the hydroxyl phosphorous acid ester, phosphinate and/or two phosphonous acid acid esters, as four (2,4-two-tert-butyl-phenyl) biphenylene two phosphinates etc.
Following embodiment illustrates the present invention.The present invention is not limited to embodiment.
Embodiment
The preparation of the solution of embodiment 1 polystyrene in hexanaphthene
117.82kg distillatory hexanaphthene is transferred to the 5001 stirred pot neutralizations that are under the nitrogen be heated to 50 ℃.In 4 hours, 48.29kg polystyrene (PS) is stirred in the adding solution then.When stirring, under 70 ℃, solution was placed 24 hours again.After cooling, under 50 ℃, under nitrogen, the MTBE (methyl tertiary butyl ether) of 53.32kg is joined in the solution.Then with the solution cool to room temperature that stirs.
Embodiment 2 uses the hydrogenation of the polystyrene of Ni catalyzer
In 401 autoclaves that are equipped with agitator, fill 21.943kg polystyrene solution (MTBE of PS+11.782kg hexanaphthene+5.332kg of 21.943kg solution=4.829 kg), be added in the 625g Ni catalyzer among 2.951 the MTBE then.Agitated autoclave is adjusted to corresponding hydrogen pressure 100 crust and when stirring reactor is heated to 160 ℃.During reaction, pressure remains on 100 crust automatically.In case termination reaction and reaction mixture being stirred 2-4 hour then when no longer further consuming hydrogen.By after removing by filter catalyzer, separate the hydrogenant polymkeric substance by evaporating solvent.
The blend of embodiment 3 HPS and polycarbonate in kneading machine
The Haake Rheomix 600 twin screw kneading machines that will link to each other with Haake Rheocord 90 processing units are heated to 290 ℃, fill 95g polycarbonate and 5g polyvinyl eyclohexane, wherein under nitrogen gas stream, use Katron-Soder T-20 metering unit and kneading to carry out 1 hour (40rpm).
The blend of embodiment 4 HPS and polycarbonate in forcing machine
Haake Rheomix TW 100 twin screw extruders that will link to each other with Haake Rheocord 90 processing units are heated to 300 ℃, fill 95g polycarbonate (Makrolon 1243) and 5g polyvinyl eyclohexane, wherein use Katron-Soder T-20 metering unit.To adopt travelling belt and cooling tank (both is Brabender OHG) to be transported to granulation unit (CF-Scheer ﹠amp by the fusion blend of circular cross section die head; Cie).
Embodiment 5
Optical haze degree and transmissivity test use 60mm * 60mm * 2mm sheet to carry out.According to ASTM-1003/290, use HazeGard (BYK-Gardner) optical haze degree instrument to carry out the test of optical haze degree.Use is equipped with the Perkin-Elmer Lambda 900 photometers record transmitted spectrum of spherical detector, and air as a reference.Table I is summed up optical haze degree and total transmittance test.
Table I
The optical haze degree and the total transmittance that comprise the polycarbonate of polymkeric substance light diffusing agent
??No. Thickness of sample (mm) The light diffusing agent that uses Concentration (wt.%) Optical haze degree (%) Total transmittance (%) at 450nm Total transmittance (%) at 700nm
??1 ??0.5 ??HPS ??1 ??17 ??82 ??87
??2 ??0.5 ??HPS ??3 ??87 ??63 ??77
??3 ??0.5 ??HPS ??5 ??＞99 ??52 ??68
??4 ??2 ??HPS ??1 ??32 ??69 ??82
??5 ??2 ??HPS ??3 ??＞99 ??32 ??54
??6 ??2 ??HPS ??5 ??＞99 ??23 ??40
??7 ??2 ??PS ??1 ??26 ??48 ??72
??8 ??2 ??Apel ??1 ??45 ??44 ??65
??9 ??2 ??Apel ??5 ??97 ??14 ??39
??10 ??2 ??Arton ??1 ??24 ??56 ??75
??11 ??2 ??Arton ??5 ??91 ??22 ??50
Embodiment 6
Stress/strain is tested at room temperature, and (170mm * 10mm * 4mm), use Instron 5566 testers carries out under 5mm/min speed to adopt no.3 dumbbell batten.Impact Test adopts 80mm * 10mm * 4mm batten to carry out.The sample that use has 2mm V breach is used for the notched Izod impact strength test.Comprise 1% and the mechanical property of the PC of 5%HPS see Table II.
Table II
Mechanical property with the polycarbonate (Makrolon 1243) of HPS blend
Performance Unit Sample A Sample B
Form wt.％ 99％PC+1％HPS ?95％PC+5％HPS
Glass transition temperature Tg ℃ 141 ?141
Flexural shock test with breach
Shock strength a when RT k kJ/m 2 7.6 ?3.5
Maximum strength when RT N 286 ?268
Fracture behaviour Brittle Brittle
There is not the flexural shock test of breach
Shock strength a when RT n kJ/m 2 213 ?213
Maximum strength when RT N 939 ?935
Fracture mode Flexible Flexible
Deformational behavior
Young's modulus MPa 1990±100 ?1960±100
Yielding stress MPa 61.0±0.1 ?61.6±0.3
Yield strain ％ 5.8±0.1 ?6.2±0.3
Tensile strength MPa 62.9±1.4 ?61.9±0.8
Elongation at break ％ 90.8±1.2 ?95.1±2.2
Embodiment 7
Extruding of double-walled sheet material
According to embodiment 5; production comprises the HPS/ polycarbonate pellet of 3wt%HPS; then in special S-70 forcing machine (Bayer AG), as double-walled sheet material (every layer of 1mm is thick), with the pellet coextrusion with thick UV protective layer of 60 μ m (Bayer AG-DP1-1244/5-55/0.54).Speed of rotation is 38rpm, and the intake zone temperature is 270 ℃, and first district's temperature is 280 ℃, and second district's temperature is 270 ℃, and the 3rd district's temperature is 260 ℃, and 4-6 district and outlet area temperature are 250 ℃.Embodiment 8
According to DIN 53 443, use hail formula (hail) test, evaluate root is according to the mechanical property of the double wall sheet of embodiment 7 productions.The diameter that employing falls from the 20mm eminence is the test piece (forming according to embodiment 6) that the ball pin of 5mm is hit the double-walled sheet material, and 50mm is wide and 350mm long.Pin is loaded with the weight of 36kg.Test is carried out under 23 ℃.Table III shows test results.
Table III
In the hail formula test of falling, (one deck=1mm) is gone up strength at break Fs, elongation at failure Ls and the failure energy Ws that measures comprising the double-walled polycarbonate sheet of 3wt%HPS.
Test Fracture behaviour ?Fs(kN) ?Ls(mm) ?Ws(J)
1 ?B ?0.42 ?14.0 ?2.46
2 ?B ?0.36 ?14.7 ?3.02
3 ?B ?0.37 ?11.3 ?2.30
4 ?A ?0.37 ?13.0 ?1.58
5 ?A ?0.45 ?13.3 ?2.50
6 ?B ?0.30 ?12.2 ?2.12
7 ?B ?0.55 ?14.1 ?3.64
8 ?B ?0.64 ?10.7 ?3.61
9 ?B ?0.52 ?10.7 ?2.53
10 ?B ?0.68 ?14.0 ?3.35
Mean value ?0.47 ?12.8 ?2.71
*A: toughness/fragility; B: smooth break
Embodiment 9
Directly extrude the double-walled sheet material from polycarbonate and HPS
In special S-70 forcing machine (Bayer AG), as double-walled sheet material (every layer of 1mm is thick) with thick UV protective layer of 60 μ m (Bayer AG-DP1-1244/5-55/054), will be less than mixing in advance polycarbonate and HPS (weight ratio 97: 3) coextrusion.Speed of rotation is 38rpm, and the intake zone temperature is 270 ℃, and first district's temperature is 280 ℃, and second district's temperature is 270 ℃, and the 3rd district's temperature is 260 ℃, and 4-6 district and outlet area temperature are 250 ℃.

Claims (10)

1. polymer composition, it comprises the polycarbonate with cycloolefin (being total to) polymer blending.
2. according to the polymer composition of claim 1, it comprises the cycloolefin of 25wt% (being total to) polymkeric substance at the most.
3. according to the polymer composition of claim 1 and/or 2, it comprises hydrogenated polystyrene or hydrogenated polystyrene multipolymer.
4. according to the polymer composition of aforementioned claim one, it is included in 300 ℃ of following melt volume-flow rate is 3-8cm 3The polycarbonate of/10min.
5. polycarbonate Alloys that comprises cycloolefin (being total to) polymkeric substance.
6. polycarbonate products or material, it comprises the polycarbonate with cycloolefin (being total to) polymer blending.
Cycloolefin (being total to) polymkeric substance in polycarbonate as the purposes of light diffusing agent.
8. the purposes that is used for light diffusion product or material produce according to the polymer composition of claim 1.
9. the purposes that is used for light diffusion product or material produce according to the polycarbonate Alloys of claim 2.
10. method by blend polycarbonate and cycloolefin (being total to) polymer production light diffusion polymer composition.
CN00814756A 1999-10-27 2000-10-16 Blended polycarbonate compositions Pending CN1382188A (en)

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CN101213256B (en) * 2005-07-05 2011-03-09 出光兴产株式会社 Light-diffusing polycarbonate resin composition and light-diffusing plate using same
CN103525065A (en) * 2013-10-26 2014-01-22 安徽省富光实业股份有限公司 Polycarbonate compound material for manufacturing cup shell and preparation method of polycarbonate compound material
CN103554882A (en) * 2013-10-26 2014-02-05 安徽省富光实业股份有限公司 Modified polycarbonate material for water cup shells and preparation method thereof
CN116622207A (en) * 2023-05-27 2023-08-22 东莞市华驰高分子材料有限公司 Protective film for screen and preparation method thereof

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KR100574092B1 (en) * 2003-08-27 2006-04-27 제일모직주식회사 Light Diffusing Thermoplastic Resin Composition
JP5334779B2 (en) * 2009-09-29 2013-11-06 ユニチカ株式会社 Resin composition and molded body comprising the resin composition

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JPS59179661A (en) * 1983-03-31 1984-10-12 Bando Chem Ind Ltd Oil-containing synthetic resin composition
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CN101213256B (en) * 2005-07-05 2011-03-09 出光兴产株式会社 Light-diffusing polycarbonate resin composition and light-diffusing plate using same
CN103525065A (en) * 2013-10-26 2014-01-22 安徽省富光实业股份有限公司 Polycarbonate compound material for manufacturing cup shell and preparation method of polycarbonate compound material
CN103554882A (en) * 2013-10-26 2014-02-05 安徽省富光实业股份有限公司 Modified polycarbonate material for water cup shells and preparation method thereof
CN116622207A (en) * 2023-05-27 2023-08-22 东莞市华驰高分子材料有限公司 Protective film for screen and preparation method thereof
CN116622207B (en) * 2023-05-27 2023-10-27 东莞市华驰高分子材料有限公司 Protective film for screen and preparation method thereof

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JP2003513134A (en) 2003-04-08
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KR20020047281A (en) 2002-06-21
AU1138501A (en) 2001-05-08
WO2001030909A1 (en) 2001-05-03

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