EP3097409A1 - Method for accelerated degradation of thermoplastics - Google Patents
Method for accelerated degradation of thermoplasticsInfo
- Publication number
- EP3097409A1 EP3097409A1 EP14703232.0A EP14703232A EP3097409A1 EP 3097409 A1 EP3097409 A1 EP 3097409A1 EP 14703232 A EP14703232 A EP 14703232A EP 3097409 A1 EP3097409 A1 EP 3097409A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- thermoplastic
- polycarbonate
- time
- discoloration
- period
- 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- Withdrawn
Links
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 134
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 134
- 238000000034 method Methods 0.000 title claims abstract description 126
- 230000015556 catabolic process Effects 0.000 title claims abstract description 35
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 35
- 239000004417 polycarbonate Substances 0.000 claims abstract description 119
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 119
- 238000002845 discoloration Methods 0.000 claims abstract description 44
- 238000000985 reflectance spectrum Methods 0.000 claims abstract description 4
- 238000000411 transmission spectrum Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 58
- -1 polyethylene terephthalate Polymers 0.000 claims description 57
- 238000009472 formulation Methods 0.000 claims description 29
- 229920000728 polyester Polymers 0.000 claims description 14
- 125000004122 cyclic group Chemical group 0.000 claims description 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 239000012080 ambient air Substances 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 67
- 125000003118 aryl group Chemical group 0.000 description 34
- 239000006085 branching agent Substances 0.000 description 32
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 28
- 239000003795 chemical substances by application Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 22
- 238000012360 testing method Methods 0.000 description 21
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 16
- 238000002834 transmittance Methods 0.000 description 16
- 229930185605 Bisphenol Natural products 0.000 description 15
- 150000001491 aromatic compounds Chemical class 0.000 description 13
- 229910052736 halogen Inorganic materials 0.000 description 13
- 150000002367 halogens Chemical group 0.000 description 13
- 238000005286 illumination Methods 0.000 description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 12
- 229920001897 terpolymer Polymers 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 125000002947 alkylene group Chemical group 0.000 description 10
- 125000005587 carbonate group Chemical group 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 8
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 150000002431 hydrogen Chemical group 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical group 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 5
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000002877 alkyl aryl group Chemical group 0.000 description 5
- 229940106691 bisphenol a Drugs 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical compound OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000000732 arylene group Chemical group 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 239000012780 transparent material Substances 0.000 description 4
- 229920006352 transparent thermoplastic Polymers 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- SJDACOMXKWHBOW-UHFFFAOYSA-N oxyphenisatine Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2NC1=O SJDACOMXKWHBOW-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 2
- DTFQULSULHRJOA-UHFFFAOYSA-N 2,3,5,6-tetrabromobenzene-1,4-diol Chemical compound OC1=C(Br)C(Br)=C(O)C(Br)=C1Br DTFQULSULHRJOA-UHFFFAOYSA-N 0.000 description 2
- VJIDDJAKLVOBSE-UHFFFAOYSA-N 2-ethylbenzene-1,4-diol Chemical compound CCC1=CC(O)=CC=C1O VJIDDJAKLVOBSE-UHFFFAOYSA-N 0.000 description 2
- YBLBHSSRHHJKEK-UHFFFAOYSA-N 3,3-bis(4-hydroxyphenyl)-2-phenylisoindol-1-one Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)N1C1=CC=CC=C1 YBLBHSSRHHJKEK-UHFFFAOYSA-N 0.000 description 2
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 2
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 description 2
- YTRKBSVUOQIJOR-UHFFFAOYSA-N 4-[2-(4-hydroxy-1-methylcyclohexa-2,4-dien-1-yl)propan-2-yl]-4-methylcyclohexa-1,5-dien-1-ol Chemical compound C1C=C(O)C=CC1(C)C(C)(C)C1(C)CC=C(O)C=C1 YTRKBSVUOQIJOR-UHFFFAOYSA-N 0.000 description 2
- QHJPJZROUNGTRJ-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)octan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCCCCC)C1=CC=C(O)C=C1 QHJPJZROUNGTRJ-UHFFFAOYSA-N 0.000 description 2
- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 2
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 125000005248 alkyl aryloxy group Chemical group 0.000 description 2
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- RGIBXDHONMXTLI-UHFFFAOYSA-N chavicol Chemical compound OC1=CC=C(CC=C)C=C1 RGIBXDHONMXTLI-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000000068 chlorophenyl group Chemical group 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- FRNQLQRBNSSJBK-UHFFFAOYSA-N divarinol Chemical compound CCCC1=CC(O)=CC(O)=C1 FRNQLQRBNSSJBK-UHFFFAOYSA-N 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229920005787 opaque polymer Polymers 0.000 description 2
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Chemical group 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001603 poly (alkyl acrylates) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 150000005691 triesters Chemical group 0.000 description 2
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- UXUFTKZYJYGMGO-CMCWBKRRSA-N (2s,3s,4r,5r)-5-[6-amino-2-[2-[4-[3-(2-aminoethylamino)-3-oxopropyl]phenyl]ethylamino]purin-9-yl]-n-ethyl-3,4-dihydroxyoxolane-2-carboxamide Chemical compound O[C@@H]1[C@H](O)[C@@H](C(=O)NCC)O[C@H]1N1C2=NC(NCCC=3C=CC(CCC(=O)NCCN)=CC=3)=NC(N)=C2N=C1 UXUFTKZYJYGMGO-CMCWBKRRSA-N 0.000 description 1
- KNUQTXWYBWMTMP-UHFFFAOYSA-N (3-hydroxyphenyl) hydrogen carbonate Chemical group OC(=O)OC1=CC=CC(O)=C1 KNUQTXWYBWMTMP-UHFFFAOYSA-N 0.000 description 1
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- DIQLMURKXNKOCO-UHFFFAOYSA-N 1,1,1',1'-tetramethyl-3,3'-spirobi[3a,7a-dihydro-2H-indene]-5,5'-diol Chemical compound CC1(C)CC2(CC(C)(C)C3C=CC(O)=CC23)C2C=C(O)C=CC12 DIQLMURKXNKOCO-UHFFFAOYSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- UNIVUTHKVHUXCT-UHFFFAOYSA-N 2,2-bis(4-hydroxyphenyl)acetonitrile Chemical compound C1=CC(O)=CC=C1C(C#N)C1=CC=C(O)C=C1 UNIVUTHKVHUXCT-UHFFFAOYSA-N 0.000 description 1
- ZSDAMBJDFDRLSS-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-diol Chemical compound OC1=C(F)C(F)=C(O)C(F)=C1F ZSDAMBJDFDRLSS-UHFFFAOYSA-N 0.000 description 1
- GFZYRCFPKBWWEK-UHFFFAOYSA-N 2,3,5,6-tetratert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=C(C(C)(C)C)C(O)=C1C(C)(C)C GFZYRCFPKBWWEK-UHFFFAOYSA-N 0.000 description 1
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- NLQBQVXMWOFCAU-UHFFFAOYSA-N 2,4,5,6-tetrafluorobenzene-1,3-diol Chemical compound OC1=C(F)C(O)=C(F)C(F)=C1F NLQBQVXMWOFCAU-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/44—Resins; Plastics; Rubber; Leather
- G01N33/442—Resins; Plastics
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
- G01N17/004—Investigating resistance of materials to the weather, to corrosion, or to light to light
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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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
Definitions
- thermoplastics such as the rate of discoloration of opaque, translucent and transparent polycarbonates, when subjected to heat and light.
- Thermoplastics comprise a large family of polymers, most of which have a high molecular weight. Intermolecular forces are responsible for the association of the molecular chains, which allows thermoplastics to be heated and remolded. Thermoplastics become pliant and moldable at a temperature above their glass transition temperature but below their melting point, and the intermolecular forces reform after molding and upon cooling of the thermoplastic, resulting in the molded product having substantially the same physical properties as the material prior to molding.
- thermoplastics to light Exposure of thermoplastics to light is known to induce changes to the polymer.
- the exposure of opaque, translucent and transparent polycarbonates to blue LED (light emitting diode) light is of interest for the manufacture of efficient illumination devices such as lamps and other types of lighting apparatuses.
- Transparent is defined as a light transmittance of at least 80% when tested in the form of a 3.2 mm thick test sample according to ASTM D 1003-00 (2000) (hereby incorporated by reference).
- Translucent is defined as a light transmittance greater than or equal to 40% when tested in the form of a 2.5 mm thick test sample according to ASTM D1003-00 (2000).
- Opaque is defined as a light transmittance of 10% or greater when tested in the form of a 3.2 mm thick test sample according to ASTM D 1003-00 (2000).
- the testing according to ASTM D 1003-00 (2000) uses procedure A and CIE illuminant C and 2 degree observer on a CE7000A using an integrating sphere with 87diffuse geometry, specular component included, UV included, large lens, and large area view, with percentage transmittance value reported as Y (luminous transmittance) taken from the CIE 1931 tristimulus values XYZ.
- Blue LED light having a peak intensity from about 400 nanometers (nm) to 500 nm and an irradiance 3,500 Watts per square meter (W/m 2 ) to about 120,000 W/m 2 is of particular interest.
- white LED light having a peak intensity from about 400 nm to about 500 nm and an irradiance less than 120,000 W/m is also of interest.
- Opaque and translucent polycarbonate may be formed, for example, using titanium dioxide compounded with the polycarbonate formulation.
- remote phosphors also known as "luminescent conversion materials”
- luminescent conversion materials include yttrium aluminum garnet (YAG) doped with rare earth elements, terbium aluminum garnet doped with rare earth elements, silicate (BOSE) doped with rare earth elements; nitrido silicates doped with rare earth elements; nitride orthosilicate doped with rare earth elements, and oxonitridoaluminosilicates doped with rare earth elements.
- Quantum dots comprising inorganic materials, usually cadmium based phosphorescent compounds may also be used to form opaque and translucent
- Translucent polycarbonates are formed using scattering agents such as light diffusers.
- the light diffusers often take the form of light diffusing particles and are used in the manufacture of articles that have good luminance.
- Such articles provide a high level of transmission of incident light (such as natural light through a window or skylight, or artificial light) with a minimum light loss by reflectance or scattering, where it is not desirable to either see the light source or other objects on the other side of the article.
- An article e.g., a sheet having a high degree of hiding power (i.e., luminance) allows a significant amount of light through, but is sufficiently diffusive so that a light source or image is not discernible through the panel.
- Light diffusers can be (meth)acrylic-based and include poly(alkyl acrylate)s and poly(alkyl methacrylate)s. Examples include
- Light diffusers also include silicones such as poly(alkylsilsesquioxanes), for example poly(alkylsilsesquioxane)s such as the
- poly(methylsilsesquioxane) available under the trade name TOSPEARLTM from Momentive Performance Materials Inc.
- the alkyl groups in the poly(alkyl acrylate)s, poly(alkylmethacrylate)s and poly(alkylsilsesquioxane)s can contain one to about twelve carbon atoms.
- Light diffusers can also be cross-linked.
- PMMA can be crosslinked with another copolymer such as polystyrene or ethylene glycol dimethacrylate.
- the polycarbonate composition comprises a light diffusing crosslinked poly(methyl methacrylate), poly(tetrafluoroethylene), poly(methylsilsesquioxane), or a combination comprising at least one of the foregoing.
- Cyclic olefin polymers and cyclic olefin co-polymers can also be used to create diffusers.
- Light diffusers also include certain inorganic materials, such as materials containing antimony, titanium, barium, and zinc, for example the oxides or sulfides of antimony, titanium, barium and zinc, or a combination containing at least one of the forgoing.
- the particle size of the diffusers can be less than or equal to 10 micrometers ( ⁇ ). For example, the particle size of
- poly(alkylsilsesquioxane)s such as poly(methylsilsesquioxane) can be 1.6 ⁇ to 2.0 ⁇ , and the particle size of crosslinked PMMA can be 3 ⁇ to 6 ⁇ .
- Light diffusing particles can be present in the polycarbonate composition in an amount of 0 to 1.5%, specifically 0.001 to 1.5%, more specifically 0.2% to about 0.8% by weight based on the total weight of the composition.
- poly(alkylsilsesquioxane)s can be present in an amount of 0 to 1.5 wt.% based on the total weight of the composition
- crosslinked PMMA can be present in an amount of 0 to 1.5 wt.% based on the total weight of the composition.
- thermoplastic formulations in particular, the rate of discoloration of opaque, translucent and transparent polycarbonate formulations when exposed to light, and thereby be able to evaluate and compare the different formulations as to their suitability for use in LED lamps. It is desirable that the method provide an accelerated test of the thermoplastic which is not too slow so as to be impractical, and not too fast, so as to destroy the samples before meaningful comparisons can be made between formulations. Such a method will permit judicious selection of polycarbonate grades for their suitability to LED lighting applications.
- the disclosure concerns a method for determining degradation of a thermoplastic, such as transparent polycarbonate.
- a method for determining degradation of a thermoplastic can comprise: illuminating the thermoplastic with light having a peak intensity centered at a wavelength from about 400 nm to about 500 nm and an irradiance from about 400 W/m to about
- a method for determining degradation of a thermoplastic comprising: illuminating the thermoplastic with light having a peak intensity centered at a wavelength from about 400 nm to about 500 nm and an irradiance from about 400 W/m to about 150,000 W/m for a first period of time; measuring temperatures of at least two samples of the thermoplastic; calculating an average temperature of the thermoplastic using the temperatures of the at least two samples of the thermoplastic; and maintaining the average temperature of the thermoplastic at a temperature from about 23°C to about 175°C during the first period of time; wherein the thermoplastic comprises polycarbonate and where the degradation is a discoloration rate.
- Figure 1 is a schematic diagram illustrating an example device for executing a method for determining degradation of a thermoplastic, such as an opaque, translucent or transparent polycarbonate.
- Figure 2 is a flow chart illustrating an example method for determining degradation of thermoplastic according to the invention.
- Figures 3 and 4 are flow charts illustrating example methods for measuring a degree of discoloration of transparent thermoplastic samples.
- FIG. 1 shows an example apparatus 10 which is useful for determining degradation of thermoplastics, in particular, for characterizing and comparing the rate of discoloration of opaque, translucent and transparent polycarbonates.
- Apparatus 10 comprises an oven chamber 12 in which a plurality of thermoplastic samples are positioned for testing. Three samples, 14, 16 and 18, each formed of a sample pair, each sample pair comprising two sample elements (14a, 14b, 16a, 16b, and 18a, 18b respectively), are shown by way of example, it being understood that more or fewer samples can be tested by the method according to the invention.
- Each sample pair 14a and 14b, 16a and 16b, 18a and 18b is illuminated by a respective light source 20, 22, 24 comprising, for example, LEDs 26 whose light emissions 28 are transmitted using silica glass waveguides 30.
- the LEDs and the waveguides work together so as to illuminate the samples with light spread over a desired range of wavelengths and intensities according to the parameters of the method described below.
- Each sample is instrumented with a respective thermometric transducer 32, for example, a thermocouple, for measuring the temperature of each sample.
- Transducers 32 generate electrical signals, for example, in the form of voltages, which are indicative of the temperature of each sample.
- Each sample pair may be heated by a respective heating element 34, 36 and 38 for example, an electrical resistance heater.
- Controller 40 may be, for example, a programmable logic controller or a computer with resident software and firmware. Controller 40 receives, manipulates and interprets temperature signals from the thermometric transducers 32 and, using this information in a feedback loop, controls the operation of the light sources 20, 22 and 24 (LEDs 26) and the heating elements 34, 36 and 38 according to the algorithms provided by its resident software. Controller 40 may also record and log data from the test. Communication between the various components and the controller 40 is effected in this example over dedicated communication lines 42.
- the samples are divided into sample pairs 14a, 14b, 16a, 16b and 18a, 18b, each having a respective illumination source 20, 22 and 24 and a respective heater 34, 36 and 38 because the method uses the average temperature derived from at least two sample elements comprising the sample pair to control operation of the respective heating elements 34, 36 and 38 for each sample pair so as to maintain the samples at a desired temperature as specified for a particular test protocol.
- each sample pair may be tested at a different temperature and irradiance from a neighboring sample.
- Apparatus 10 can thus test samples of different materials, wherein each sample element in a sample pair is comprised of the same material, i.e., sample elements 14a and 14b are the same material, sample elements 16a and 16b are the same material (but not necessarily the same as sample elements 14a and 14b). Controller 40 calculates the average temperatures of the sample pairs and uses this information to control the heating elements 34, 36 and 38. The samples are cooled by natural circulation of air within the oven chamber 12. Fans may also be used for a forced circulation regime if necessary.
- FIG. 2 is a flow chart which outlines an example method of determining degradation of opaque, translucent and transparent thermoplastics according to the invention.
- each thermoplastic sample such as a transparent polycarbonate of a first formulation
- sample pair comprising two sample elements.
- sample, sample pair and sample elements refer to a sample material being tested.
- Each sample pair is respectively illuminated with light for a desired period of time as noted at box 44.
- illuminating light having its peak intensity centered at a wavelength from about 400 nm to about 500 nm and having an irradiance from about 400 W/m to about 150,000 W/m (calibration for all irradiance values via a power meter such as the Model UP 55N 40S-H9 marketed by GENTEC-EO USA Inc. of Lake Oswego, Oregon).
- the temperature of each sample pair is maintained at a respective desired temperature, for example, from about 23°C to about 175°C for the desired period of time.
- the sample pair temperature is maintained by measuring the temperatures of at least two sample elements, calculating the average temperature of these two sample elements, and using that average temperature to control the heating and cooling of each sample pair.
- the data derived from this test can be used to determine a rate of degradation of the samples, as well as for comparative purposes with other samples having different formulations. For transparent materials, irradiance from about 50,000 W/m 2 to about 150,000 W/m 2 , as well as 50,000 W/m 2 to about 110,000
- W/m is also believed to be useful, as is an irradiance of about 75,000 W/m .
- Sample temperatures from about 90°C to about 130°C are also believed to be useful, as are sample temperatures of about 120°C as well as 130°C.
- W/m" to about 50,000 W/m are believed to be useful, as is an irradiance of about 3,500 W/m .
- Sample temperatures from about 23°C to about 130°C are also believed to be useful, as are sample temperatures of about 90°C.
- illuminating light wavelengths wherein the peak intensity of the light is centered from about 410 nm to about 480 nm (measured
- radiometrically are believed to be useful, as is illuminating light having its peak intensity centered at about 447 nm (measured radiometrically). These parameters are expected to allow for an illumination time period of as much as 100 hours, resulting in a measurable discoloration of the transparent polycarbonate without destroying the samples. It is further expected that illuminating light having its peak intensity centered at about 459 nm (measured radiometrically) will be useful as well as illuminating light emitted from an LED source and centered at about 470 nm dominant wavelength (measured photometrically) and about 550 nm measured radiometrically.
- Cooling of each sample may be accomplished, for example, by providing a separation distance between the sample and the light source sufficient to permit circulation of the ambient air around the sample and thereby allow convective cooling.
- Other methods of cooling such as forced air cooling using a fan for example, are also feasible.
- the step of evaluating the degradation of the sample is noted in box 50.
- This evaluation step may be accomplished, for example, by a simple visual observation of the samples, or photographs of the samples. Measurement techniques are also useful, as explained in detail below with reference to Figures 3 and 4.
- the illuminating, maintaining and evaluating steps may be repeated for a plurality of successive time periods to provide, for example, the rate of
- discoloration of a polycarbonate sample as a function of time over which it is illuminated. This may show, for example, whether the rate of discoloration increases, decreases, or remains the same over time as it is exposed to the light.
- the successive time periods may be equal to one another.
- the method comprising the illuminating, maintaining and evaluating steps may be repeated for a plurality of successive time periods for a plurality of different thermoplastic samples having different formulations. This will permit a comparative evaluation between different polycarbonate formulations to determine their relative suitability for various applications, such as for use with LED lamps and luminaries (full lighting fixtures) as noted below.
- measurement of the transparent thermoplastic degradation in this example discoloration of the transparent polycarbonate
- discoloration of the transparent polycarbonate is effected by illuminating the samples with white light after the desired time period has elapsed, and generating a transmission spectrum from a portion of the white light transmitted through the sample.
- the samples are illuminated with white light after the desired time period has elapsed and a reflectance spectrum is generated from the portion of the white light reflected from the sample. Either spectrum is expected to provide a useful measure of the discoloration of a transparent thermoplastic such as polycarbonate.
- the measurement method shown in Figure 4 could also be effectively applied to opaque and translucent thermoplastics.
- a quantitative evaluation of the discoloration may be determined using either the Yellowness Index or the CIE L*a*b color system.
- the Yellowness Index is governed by two standards, ASTM E313 (2010) for opaque materials, and ASTM D1925 (1995), for transparent materials.
- ASTM E313 (2010) for opaque materials
- ASTM D1925 (1995) for transparent materials
- YI is calculated according to the formula:
- X, Y and Z are tristimulus values for CIE illuminant C and the 1931 CIE 2° standard observer. Numerical values for a particular sample are obtained using a commercially available spectrophotometer, such as the X-Rite ⁇ Spectrophotometer marketed by X-Rite of Grand Rapids Michigan.
- the example method outlined in Figures 2-4 may be used to gather data on a plurality of different polycarbonate formulations and then compare the discoloration rates of the various different formulations to determine which might be suitable for use in LED lighting, those sample polycarbonate formulations having the slowest discoloration rate being
- Testing methods using the parameters outlined herein have permitted illumination time periods of 100 hours for transparent materials and have been used to evaluate numerous different samples to determine and compare their discoloration rates.
- Ranges articulated within this disclosure shall include disclosure for possession purposes and claim purposes of the individual points within the range, sub-ranges, and combinations thereof.
- the pKa for methyl-p-hydroxybenzoate was obtained from the following reference: Chromatographia Vol. 39, No. 5/6, September 1994.
- the pKa value for p- cumylphenol was approximated based on the values of similar structures.
- the plastic material of the plastic composition can comprise a polycarbonate. Descriptions of the various types of polycarbonates are articulated below, but should not be construed as limiting.
- the polycarbonates have repeating structural carbonate units of the formula (1):
- the polycarbonate is derived from bisphenol-A.
- each R 1 group is a divalent aromatic group, for example derived from an aromatic dihydroxy compound of the formula (2):
- each of A 1 and A 2 is a monocyclic divalent arylene group
- Yl is a single bond or a bridging group having one or two atoms that separate A 1 from A 2.
- one atom separates A 1 from A2.
- Y 1 is para to each of the hydroxyl groups on the phenylenes.
- Illustrative non-limiting examples of groups of this type are -0-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, methylene, cyclohexyl-methylene, 2- [2.2.1]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene, and adamantylidene.
- the bridging group Y 1 can be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene, or isopropylidene.
- R a and R b each represent a halogen atom or a monovalent hydrocarbon group and can be the same or different; p and q are each independently integers of 0 to 4; and X a represents a single bond or one of the groups of formulas (4) or (5):
- R c and R d are each independently hydrogen, C 1-12 alkyl, C 1-12 cycloalkyl, C 7 _i 2 arylalkyl,
- R c and R d are each the same hydrogen or C 1-4 alkyl group, specifically the same C 1-3 alkyl group, even more specifically, methyl.
- R c and R d taken together represent a C 3 _ 2 o cyclic alkylene group or a heteroatom-containing C 3 _ 2 o cyclic alkylene group comprising carbon atoms and heteroatoms with a valency of two or greater.
- These groups can be in the form of a single saturated or unsaturated ring, or a fused polycyclic ring system wherein the fused rings are saturated, unsaturated, or aromatic.
- a specific heteroatom-containing cyclic alkylene group comprises at least one heteroatom with a valency of 2 or greater, and at least two carbon atoms.
- heteroatoms in the heteroatom-containing cyclic alkylene group include -0-, -S-, and -N(Z)-, where Z is a substituent group selected from hydrogen, hydroxy, C 1-12 alkyl, C 1-12 alkoxy, or C 1-12 acyl.
- X a is a substituted C 3-18 cycloalkylidene of the formula 6):
- each R r , R p , R q , and R 1 is independently hydrogen, halogen, oxygen, or C 1-12 organic group;
- I is a direct bond, a carbon, or a divalent oxygen, sulfur, or -N(Z)- wherein Z is hydrogen, halogen, hydroxy, C 1-12 alkyl, C 1-12 alkoxy, or C 1-12 acyl;
- h is 0 to 2
- j is 1 or 2
- i is an integer of 0 or 1
- k is an integer of 0 to 3, with the proviso that at least two of R r , R p , R q , and R 1 taken together are a fused cycloaliphatic, aromatic, or heteroaromatic ring.
- the ring as shown in formula (6) will have an unsaturated carbon-carbon linkage where the ring is fused.
- the ring as shown in formula (6) contains 4 carbon atoms
- the ring as shown in formula (6) contains 5 carbon atoms
- the ring contains 6 carbon atoms.
- two adjacent groups e.g., R q and R 1 taken together
- R q and R 1 taken together form one aromatic group
- R r and R p taken together form a second aromatic group.
- Non-limiting examples of dihydroxy compounds that can provide polycarbonates with glass transition temperatures (Tgs) greater than 170°C include 3,3-bis(4-hydroxyphenyl)-2- phenylisoindolin-l-one (PPPBP), l,l-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane) (Bisphenol TMC), 4,4'-(l-phenylethane-l,l-diyl)diphenol (bisphenol AP) as well as adamantyl containing aromatic dihydroxy compounds and fluorene containing aromatic dihydroxy compounds.
- Tgs glass transition temperatures
- dihydroxy compounds of formula (2) may be the following formul
- dihydroxy compounds of formula (2) may be the following formula (
- a polycarbonate can have a bisphenol of formula (D) as a repeating monomer unit therein:
- each R is independently hydrogen, C 1-12 alkyl, or halogen; and each R g is independently hydrogen or C 1-12 alkyl.
- the substituents can be aliphatic or aromatic, straight chain, cyclic, bicyclic, branched, saturated, or unsaturated.
- Such cyclohexane-containing bisphenols for example the reaction product of two moles of a phenol with one mole of a hydrogenated isophorone, are useful for making polycarbonate polymers with high glass transition
- polycarbonates or a combination comprising at least one of the foregoing with other bisphenol polycarbonates, are supplied by Bayer Co. under the APEC® trade name.
- each R h is independently a halogen atom, a Ci_io hydrocarbyl such as a Ci_io alkyl group, a halogen substituted Ci-iohydrocarbyl such as a halogen-substituted C MO alkyl group, and n is 0 to 4.
- the halogen is usually bromine.
- dihydroxy compounds include the following: 4,4'- dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4- hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)- 1 - naphthylmethane, l,2-bis(4-hydroxyphenyl)ethane, l,l-bis(4-hydroxyphenyl)-l-phenylethane, 2- (4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2- bis(4-hydroxy-3-bromophenyl)propane, 1,1 -bis (hydroxyphenyl)cyclopentane, l,l-bis(4- hydroxyphenyl)cyclohexane, 1 , 1 -bis(4-
- bisphenol compounds that can be represented by formula (2) include l,l-bis(4-hydroxyphenyl) methane, l,l-bis(4-hydroxyphenyl) ethane, 2,2-bis(4- hydroxyphenyl) propane (hereinafter "bisphenol A” or "BPA”), 2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane, l,l-bis(4-hydroxyphenyl) propane, l,l-bis(4- hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-l-methylphenyl) propane, l,l-bis(4-hydroxy-t- butylphenyl) propane, 3,3-bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3-bis(4- hydroxyphenyl) phthalimidine (PPPBP), and l,l-bis(4-hydroxy-3-methylphenyl)
- Polycarbonate as used herein includes homopolycarbonates, copolymers comprising different R 1 moieties in the carbonate (also referred to herein as “copolycarbonates”), and copolymers comprising carbonate units and other types of polymer units, such as ester units.
- the polycarbonate is a linear homopolymer or copolymer comprising units derived from bisphenol A, in which each of A 1 and A2 is p-phenylene and Y 1 is isopropylidene in formula (2). More specifically, greater than or equal to 60%, particularly greater than or equal to 80% of the R 1 groups in the polycarbonate are derived from bisphenol A.
- Another specific type of copolymer is a polyester carbonate, also known as a polyester-polycarbonate. Such copolymers further contain, in addition to recurring carbonate chain units of the formula (1), repeating units of formula (9):
- D is a divalent group derived from a dihydroxy compound, and can be, for example, a C 2 - Cio alkylene group, a C 6 - C 20 alicyclic group, a C 6 - C 20 aromatic group or a
- D is a C 2 to C30 alkylene group having a straight chain, branched chain, or cyclic (including polycyclic) structure.
- D is derived from an aromatic dihydroxy compound of formula (3) above.
- D is derived from an aromatic dihydroxy compound of formula (8) above.
- aromatic dicarboxylic acids that can be used to prepare the polyester units include isophthalic or terephthalic acid, l,2-di(p-carboxyphenyl)ethane, 4,4'- dicarboxydiphenyl ether, 4,4'-bisbenzoic acid, and combinations comprising at least one of the foregoing acids. Acids containing fused rings can also be present, such as in 1,4-, 1,5-, or 2,6- naphthalenedicarboxylic acids. Specific dicarboxylic acids are terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, or combinations thereof.
- a specific dicarboxylic acid comprises a combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98.
- D is a C 2 _ 6 alkylene group and T is p-phenylene, m-phenylene, naphthalene, a divalent cycloaliphatic group, or a combination thereof.
- This class of polyester includes the poly(alkylene terephthalates).
- the molar ratio of ester units to carbonate units in the copolymers can vary broadly, for example 1:99 to 99:1, specifically 10:90 to 90:10, more specifically 25:75 to 75:25, depending on the desired properties of the final composition.
- the polyester unit of a polyester-polycarbonate can be derived from the reaction of a combination of isophthalic and terephthalic diacids (or derivatives thereof) with resorcinol.
- the polyester unit of a polyester- polycarbonate is derived from the reaction of a combination of isophthalic acid and terephthalic acid with bisphenol-A.
- the polycarbonate units are derived from bisphenol A.
- the polycarbonate units are derived from resorcinol and bisphenol A in a molar ratio of resorcinol carbonate units to bisphenol A carbonate units of 1:99 to 99:1.
- a specific example of a polycarbonate-polyester is a copolycarbonate-polyester- polysiloxane terpolymer comprising carbonate units of formula (1), ester units of formula (9), and pol siloxane (also referred to herein as "polydiorganosiloxane”) units of formula (10):
- R is same or different, and is a C 1-13 monovalent organic group.
- R may independently be a C 1-13 alkyl group, C 1-13 alkoxy group, C 2-13 alkenyl group, C 2 _ 13 alkenyloxy group, C 3 _ 6 cycloalkyl group, C 3 _6 cycloalkoxy group, C 6 -i4 aryl group, C 6-1 o aryloxy group, C 7-13 arylalkyl group, C 7-13 arylalkoxy group, C 7-13 alkylaryl group, or C 7-13 alkylaryloxy group.
- the foregoing groups may be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. Combinations of the foregoing R groups may be used in the same copolymer.
- the polysiloxane comprises R groups that have a minimum hydrocarbon content.
- an R group with a minimum hydrocarbon content is a methyl group.
- E in formula (10) may vary widely depending on the type and relative amount of each component in the plastic (e.g., thermoplastic) composition, the desired properties of the composition, and like considerations.
- E has an average value of 5 to 200, with the specific amount chosen so that a 1.0 mm thick plaque of the plastic composition (i.e., plastic material, coated conversion material(s), any additive(s)) has a transparency (%T) of greater than or equal to 30%.
- the E value is chosen (e.g., adjusted such as when the amount of siloxane in the material and when the siloxane is introduced to form the material and/or the process for making the material) to achieve a balance between transparency, flame retardancy, and impact.
- E has an average value of 16 to 50, specifically 20 to 45, and more specifically 25 to 45.
- E has an average value of 4 to 15, specifically 5 to 15, more specifically 6 to 15, and still more specifically 7 to 12.
- polydiorganosiloxane units are derived from dihydroxy aromatic com ound of formula (11):
- each R may independently be the same or different, and is as defined above; and each Ar may independently be the same or different, and is a substituted or unsubstituted C 6 -3o arylene group, wherein the bonds are directly connected to an aromatic moiety.
- Suitable Ar groups in formula (11) may be derived from a C 6 -3o dihydroxy aromatic compound, for example a dihydroxy aromatic compound of formula (2), (3), (7), or (8) above. Combinations comprising at least one of the foregoing dihydroxy aromatic compounds may also be used.
- dihydroxy aromatic compounds examples include resorcinol (i.e., 1,3- dihydroxybenzene), 4-methyl-l,3-dihydroxybenzene, 5-methyl-l,3-dihydroxybenzene, 4,6- dimethyl-l,3-dihydroxybenzene, 1,4-dihydroxybenzene, l,l-bis(4-hydroxyphenyl) methane, 1,1- bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane, l,l-bis(4-hydroxyphenyl) propane, l,l-bis(4- hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-l-methylphenyl) propane, l,l-bis(4- hydroxyphenyl) cyclohexane, bis(4-hydroxyphenyl sulfide
- dihydroxy aromatic compound is unsubstituted, or is not substituted with non-aromatic hydrocarbon-containing substituents such as, for example, alkyl, alkoxy, or alkylene substituents.
- polydiorganosiloxane repeating units are derived from dihydroxy aromatic compounds of formula (12):
- polydiorganosiloxane units are derived from dihydroxy aromatic com ound of formula (14):
- R and E are as described above, and each occurrence of R is independently a divalent Ci-30 alkylene or C7-30 arylene-alkylene, and wherein the polymerized polysiloxane unit is the reaction residue of its corresponding dihydroxy aromatic compound.
- R is C 7 _ 3 o arylene-alkylene
- the polydiorganosiloxane units are derived from dihydroxy aromatic com ound of formula (15):
- R and E are as defined above.
- Each R is independently a divalent C 2 -8 aliphatic group.
- Each M may be the same or different, and may be a halogen, cyano, nitro, Ci_8 alkylthio, Ci_8 alkyl, Ci_g alkoxy, C 2 -8 alkenyl, C 2 -8 alkenyloxy group, C 3 _s cycloalkyl, C 3 _s cycloalkoxy, C 6 -io aryl, C 6 -io aryloxy, C 7 _i 2 arylalkyl, C 7 _i 2 arylalkoxy, C 7 _i 2 alkylaryl, or C 7 _i 2 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.
- M is bromo or chloro, an alkyl group such as methyl, ethyl, or propyl, an alkoxy group such as methoxy, ethoxy, or propoxy, or an aryl group such as phenyl, chlorophenyl, or tolyl;
- R is a dimethylene, trimethylene or tetramethylene group; and
- R is a Ci_g alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl.
- R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl.
- M is methoxy
- n is 0 or 1
- R is a divalent Ci_ 3 aliphatic group
- R is methyl.
- the polydiorganosiloxane units are derived from a dihydroxy aromatic compound of formula (16):
- polydiorganosiloxane units are derived from dihydroxy aromatic compound of formula (17):
- Dihydroxy polysiloxanes typically can be made by functionalizing a substituted siloxane oli omer of formula (18):
- R and E are as previously defined, and Z is H, halogen (CI, Br, I), or carboxylate.
- carboxylates examples include acetate, formate, benzoate, and the like.
- compounds of formula (18) may be prepared by platinum catalyzed addition with an aliphatically unsaturated monohydric phenol.
- aliphatically unsaturated monohydric phenols examples include eugenol, 2-allylphenol, 4-allylphenol, 4-allyl-2- methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, 4-allyl-2-t-butoxyphenol, 4- phenyl-2-allylphenol, 2-methyl-4-propenylphenol, 2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo- 6-methylphenol, 2-allyl-6-methoxy-4-methylphenol, and 2-allyl-4,6-dimethylphenol.
- Combinations comprising at least one of the foregoing may also be used.
- Z is halogen or carboxylate
- functionalization may be accomplished by reaction with a dihydroxy aromatic compound of formulas (2), (3), (7), (8), or a combination comprising at least one of the foregoing dihydroxy aromatic compounds.
- compounds of formula (12) may be formed from an alpha, omega-bisacetoxypolydiorangonosiloxane and a dihydroxy aromatic compound under phase transfer conditions.
- a copolycarbonate terpolymer can be used.
- Specific copolycarbonate terpolymers include those with polycarbonate units of formula (1) wherein R 1 is a C 6 -3o arylene group, polysiloxane units derived from siloxane diols of formula (13), (16) or (17), and polyester units wherein T is a C 6 -3o arylene group.
- T is derived from isophthalic and/or terephthalic acid, or reactive chemical equivalents thereof.
- R 1 is derived from the carbonate reaction product of a resorcinol of formula (8), or a combination of a resorcinol of formula (8) and a bisphenol of formula (4).
- the polycarbonate -polyester-polysiloxane terpolymer can comprise siloxane units in an amount of 0.1 to 25 weight percent (wt%), specifically 0.2 to 10 wt , more specifically 0.2 to 6 wt , even more specifically 0.2 to 5 wt , and still more specifically 0.25 to 2 wt , based on the total weight of the polycarbonate-polyester-polysiloxane terpolymer, with the proviso that the siloxane units are provided by polysiloxane units covalently bonded in the polymer backbone of the polycarbonate-polyester-polysiloxane terpolymer.
- the polycarbonate-polyester-polysiloxane terpolymer can further comprise 0.1 to 49.85 wt carbonate units, 50 to 99.7 wt ester units, and 0.2 to 6 wt polysiloxane units, based on the total weight of the polysiloxane units, ester units, and carbonate units.
- the polycarbonate -polyester-polysiloxane terpolymer comprises 0.25 to 2 wt polysiloxane units, 60 to 96.75 wt ester units, and 3.25 to 39.75 wt carbonate units, based on the total weight of the polysiloxane units, ester units, and carbonate units.
- the specific amount of terpolymer and the composition of the terpolymer will be chosen so that a 1.0 mm thick plaque of the composition transparency (%T) of greater than or equal to 30%.
- a method of making an article of manufacture that has a V0 94 rating at a thickness of 2.0 mm comprises: (a) providing a polycarbonate, wherein the polycarbonate has a repeating structural background of the following formula
- R 1 groups wherein greater than or equal to 60 percent of the total number of R 1 groups contain aromatic organic groups and the balance thereof are aliphatic, alicyclic, or aromatic groups; an end capping agent; a branching agent; (b) selecting the end-capping agent based upon the molecular weight of the polycarbonate and the branching level imparted by the branching agent, wherein the MVR of the polycarbonate is 1 to 15 cubic centimeter per 10 minutes (cm /10 min) and wherein the pKa of the end-capping agent is 8.3 to 11; (c) forming a polycarbonate containing the end-capping agent and the branching that has a peak melt viscosity of greater than or equal to 8,000 poise when measured using a parallel plate melt rheology test at a heating rate of 10°C/min at a temperature of 350°C to 450°C; and (d) blending a conversion material and a flame retardant with the formed polycarbonate.
- the peak melt viscosity can be greater than or equal to 25,000 poise when measured using a parallel plate melt rheology test at a heating rate of 10°C/min at a temperature of 350°C to 450°C.
- the composition comprises: a flame retardant; a conversion material; a polycarbonate, wherein the polycarbonate has a repeating structural background of the following formula
- R 1 groups wherein greater than or equal to 60 percent of the total number of R 1 groups contain aromatic organic groups and the balance thereof are aliphatic, alicyclic, or aromatic groups and wherein the polycarbonate contains one or more bisphenols; wherein the polycarbonate comprises an end- capping agent; wherein the polycarbonate comprises a branching agent; and wherein the polycarbonate containing the branching agent and the end-capping agent has a peak melt viscosity of greater than or equal to 7,000 poise when calculated from the equation of wherein the peak melt viscosity equals: -57135.91 + 36961.39 * BL + 14001.13 * MW 1/J - 46944.24 * pKa - 322.51 * BL* MW 1/3 - 2669.19 * BL* pKa + 215.83 * MW 1/3 * pKa + 1125.63 * BL 2 -
- BL is the mole ratio of the branching agent in the formulation determined by dividing the number of moles of branching agent by the total number of moles of bisphenol or bisphenols in the composition
- MW is the weight- averaged molecular weight of the polycarbonate containing the branching agent and the end-capping agent as determined by gel permeation chromatography using polycarbonate standards
- pKa is the pKa of the end capping agent
- the peak melt viscosity is greater than or equal to 25,000 as calculated by the above equation.
- a method of making an article of manufacture that has a V0 94 rating at a thickness 1.5 mm comprises: (a) providing a polycarbonate, wherein the polycarbonate has a repeating structural background of the following formula
- R 1 groups wherein greater than or equal to 60 percent of the total number of R 1 groups contain aromatic organic groups and the balance thereof are aliphatic, alicyclic, or aromatic groups and wherein the polycarbonate contains one or more bisphenols; an end capping agent that is not
- the peak melt viscosity is greater than or equal to 25,000 poise calculated from the above equation.
- the polycarbonates herein may include branched polycarbonate(s).
- Various types of branching agents can be utilized for the embodiments encompassed by this disclosure.
- Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization.
- branching agents include polyfunctional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures of the foregoing functional groups.
- trimellitic acid trimellitic anhydride
- trimellitic trichloride trimellitic trichloride
- THPE tris-p-hydroxy phenyl ethane
- THPE tris-p-hydroxy phenyl ethane
- THPE tris-p-hydroxy phenyl ethane
- PA tris-phenol PA
- PA 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid.
- the branching agents can be added at a level of 0.05 to 2.0 wt .
- Mixtures comprising linear polycarbonates and branched
- polycarbonates can be used.
- a particular type of branching agent is used to create branched polycarbonate materials. These branched polycarbonate materials have statistically more than two end groups.
- the branching agent is added in an amount (relative to the bisphenol monomer) that is sufficient to achieve the desired branching content, that is, more than two end groups.
- the molecular weight of the polymer may become very high upon addition of the branching agent and may lead to viscosity problems during phosgenation. Therefore, in some embodiments, an increase in the amount of the chain termination agent is used in the
- the branching agent is a structure derived from a triacid trichloride of the formula (19):
- Z is hydrogen, a halogen, Ci_ 3 alkyl group, Ci_ 3 alkoxy group, C 7 _i 2 arylalkyl, alkylaryl, or nitro group, and z is 0 to 3; or a branching agent derived from a reaction with a tri-substituted phenol of the formula (20):
- T is a C 1-2 o alkyl group, C 1-2 o alkyleneoxy group, C 7-12 arylalkyl, or alkylaryl group
- S is hydrogen, a halogen, C 1-3 alkyl group, C 1-3 alkoxy group, C 7-12 arylalkyl, alkylaryl, or nitro group
- s is 0 to 4.
- the branching agent is a structure having formula (21):
- TMTC trimellitic trichloride
- THPE tris-p-hydroxy phenyl ethane
- isatin-bis-phenol examples include trimellitic trichloride (TMTC), tris-p-hydroxy phenyl ethane (THPE) and isatin-bis-phenol.
- Z is hydrogen and z is 3.
- S is hydrogen, T is methyl, and s is 4.
- the relative amount of branching agents used in the manufacture of the polymer will depend on a number of considerations, for example the type of R 1 groups, the amount of cyanophenol, and the desired molecular weight of the polycarbonate.
- the amount of branching agent is effective to provide about 0.1 to 10 branching units per 100 R 1 units, specifically about 0.5 to 8 branching units per 100 R 1 units, and more specifically about 0.75 to 5 branching units per 100 R 1 units.
- the amount of branching agent tri-ester groups are present in an amount of about 0.1 to 10 branching units per 100 R 1 units, specifically about 0.5 to 8 branching units per 100 R 1 units, and more specifically about 0.75 to 5 tri-ester units per 100 R 1 units.
- the amount of branching agent tricarbonate groups are present in an amount of about 0.1 to 10 branching units per 100 R 1 units, specifically about 0.5 to 8 branching units per 100 R 1 units, and more specifically about 0.75 to 5 tri-phenylcarbonate units per 100 R 1 units. In some
- a combination of two or more branching agents may be used.
- the polycarbonate of the composition has a branching level of greater than or equal to 1%, or greater than or equal to 2%, or greater than or equal to 3%, or 1% to 3%.
- end-capping agents can be utilized herein provided that such agents do not significantly adversely affect the desired properties of the compositions, such as transparency, ductility, fire retardants, and the like.
- Examples of endcapping agents include certain mono-phenolic compound(s), and/or mono-carboxylic acid chloride(s), and/or mono- chloroformate(s).
- Mono-phenolic chain stoppers are exemplified by monocyclic phenols such as phenol and Ci_C 2 2 alkyl-substituted phenols such as p-cumyl-phenol, and p-t-butyl phenol; and monoethers of diphenols, such as p-methoxyphenol, phenols with phenols with cyano- substitution such as p-cyanophenol, or with halogen substitution such as p-fluorophenol, or with nitro-substitution such as 4-nitrophenol.
- Alkyl-substituted phenols with branched chain alkyl substituents having 8 to 9 carbon atoms can be specifically mentioned.
- Certain mono-phenolic UV absorbers can also be used as an endcapping agent, for example 4-substituted-2- hydroxybenzophenones and their derivatives, aryl salicylates, monoesters of diphenols such as resorcinol monobenzoate, 2-(2-hydroxyaryl)-benzotriazoles and their derivatives, 2-(2- hydroxyaryl)-l,3,5-triazines and their derivatives, and the like.
- the polycarbonate can have an end-cap comprising phenol, such as alkyl- substituted phenols, ether-substituted phenols, ester-substituted phenols, cyano-substituted phenols, and halogen substituted phenols, as well as combinations comprising at least one of the foregoing.
- the end-capping agents can be selected from: cyanophenol and a phenol containing substitution(s) with aliphatic groups, olefinic groups, aromatic groups, halogens, ester groups, ether groups, and combinations comprising at least one of the foregoing.
- the end-capping agents can be phenol, e.g., specifically, can be selected from: cyanophenol, para-t-butylphenol, para-cumylphenol, and combinations comprising at least one of the foregoing.
- thermoplastic material to which the method may be applied include polyethylene terephthalates (PET) and polybutylene terephthalate (PBT), polyethylene napthalate (PEN), polymethyl methacrylate (PMMA), polystyrene (PS), cyclic olefinic polymers (COP) and cyclic olefinic copolymers (COC), polyetherimide as well as polycarbonate/polyester blends.
- PET polyethylene terephthalates
- PBT polybutylene terephthalate
- PEN polyethylene napthalate
- PMMA polymethyl methacrylate
- PS polystyrene
- COP cyclic olefinic polymers
- COC cyclic olefinic copolymers
- polyetherimide as well as polycarbonate/polyester blends.
- the method may also be used to test silicone based compounds as provided by Dow Corning.
- Embodiment 1 A method for determining degradation of a thermoplastic, the method comprising: illuminating the thermoplastic with light having a peak intensity centered at a wavelength from about 400 nm to about 500 nm and an irradiance from about 400 W/m to about 150,000 W/m for a first period of time; measuring temperatures of at least two samples of the thermoplastic; calculating an average temperature of the thermoplastic using the temperatures of the at least two samples of the thermoplastic; maintaining the average temperature of the thermoplastic at a temperature from about 23°C to about 175°C during the first period of time; and repeating the illuminating and maintaining steps for a plurality of successive periods of time.
- Embodiment 2 The method according to Embodiments 1, wherein the degradation comprises a discoloration rate of the thermoplastic.
- Embodiment 3 The method according to any of Embodiments 1-2, wherein the thermoplastic comprises polyethylene terephthalate (PET).
- Embodiment 4 The method according to any of Embodiments 1-3, wherein the thermoplastic comprises polybutylene terephthalate (PBT).
- Embodiment 5 The method according to any of Embodiments 1-4, wherein the thermoplastic comprises polyethylene napthalate (PEN).
- PEN polyethylene napthalate
- Embodiment 6 The method according to any of Embodiments 1-5, wherein the thermoplastic comprises polymethyl methacrylate (PMMA).
- PMMA polymethyl methacrylate
- Embodiment 7 The method according to any of Embodiments 1-6, wherein the thermoplastic comprises polystyrene (PS).
- PS polystyrene
- Embodiment 8 The method according to any of Embodiments 1-7, wherein the thermoplastic comprises cyclic olefinic polymers (COP).
- COP cyclic olefinic polymers
- Embodiment 9 The method according to any of Embodiments 1-8, wherein the thermoplastic comprises cyclic olefinic copolymers (COC).
- COC cyclic olefinic copolymers
- Embodiment 10 The method according to any of Embodiments 1-9, wherein the thermoplastic comprises polyetherimide.
- Embodiment 11 The method according to any of Embodiments 1-10, wherein the thermoplastic comprises polycarbonate.
- Embodiment 12 The method according to any of Embodiments 1-11, wherein the thermoplastic comprises polyester blends.
- Embodiment 13 The method according to any of Embodiments 1-12, wherein the thermoplastic comprises polycarbonate/polyester blends.
- Embodiment 14 The method according to any of Embodiments 1-2, wherein the thermoplastic is a polycarbonate.
- Embodiment 15 A method for determining degradation of a thermoplastic, the method comprising: illuminating the thermoplastic with light having a peak intensity centered at a wavelength from about 400 nm to about 500 nm and an irradiance from about 400 W/m to about 150,000 W/m for a first period of time; measuring temperatures of at least two samples of the thermoplastic; calculating an average temperature of the thermoplastic using the temperatures of the at least two samples of the thermoplastic; and maintaining the average temperature of the thermoplastic at a temperature from about 23°C to about 175°C during the first period of time; wherein the thermoplastic comprises polycarbonate and where the degradation is a discoloration rate.
- Embodiment 16 The method according to Embodiment 15, further comprising: repeating the illuminating, maintaining and measuring steps for a plurality of different polycarbonate formulations; and comparing the discoloration of the plurality of different polycarbonate formulations with one another.
- Embodiment 17 The method according to any of Embodiments 15-16, further comprising: repeating the illuminating and maintaining steps for a second period of time; after the second period of time has elapsed, measuring a degree of discoloration of the thermoplastic.
- Embodiment 18 The method according to any of Embodiments 15-17, further comprising comparing the degree of discoloration measured after the first period of time with the degree of discoloration after the second period of time.
- Embodiment 19 The method according to any of Embodiments 17-18, wherein the second period of time equals the first period of time in duration.
- Embodiment 20 The method according to any of Embodiments 15-19, further comprising repeating the illuminating and maintaining steps for a plurality of successive periods of time.
- Embodiment 21 The method according to any of Embodiments 1-14 and 20, further comprising evaluating the degradation of the thermoplastic after each the successive period of time.
- Embodiment 22 The method according to any of Embodiments 20-21, further comprising: repeating the illuminating, maintaining and evaluating steps for a plurality of successive time periods for a plurality of different thermoplastic formulations; and comparing the degradation of the plurality of different thermoplastic formulations with one another.
- Embodiment 23 The method according to any of Embodiments 1-14 and 20, further comprising comparing the degree of discoloration measured after each of the successive periods of time with one another.
- Embodiment 24 The method according to any of Embodiments 1-14 and 20-23, wherein each of the successive periods of time is equal in duration.
- Embodiment 25 The method according to any of Embodiments 1-14 and 20-24, wherein each of the successive periods of time is about 100 hours in duration.
- Embodiment 26 The method according to any of Embodiments 1-25, wherein evaluating the degradation comprises visually inspecting the thermoplastic.
- Embodiment 27 The method according to any of Embodiments 1-26, wherein evaluating the degradation comprises measuring a degree of discoloration of the thermoplastic.
- Embodiment 28 The method according to any of Embodiments 1-27, wherein the irradiance is from about 50,000 W/m 2 to about 150,000 W/m 2 .
- Embodiment 29 The method according to any of Embodiments 1-28, wherein the irradiance is from about 400 W/m 2 to about 50,000 W/m 2.
- Embodiment 30 The method according to any of Embodiments 1-28, wherein the irradiance is about 75,000 W/m .
- Embodiment 31 The method according to any of Embodiments 1-30, wherein the peak intensity of the light is centered at a wavelength from about 410 nm to about 480 nm.
- Embodiment 32 The method according to any of Embodiments 1-31, wherein the peak intensity of the light is centered at a wavelength of about 447 nm.
- Embodiment 33 The method according to any of Embodiments 1-32, wherein the average temperature of the polycarbonate is maintained at a temperature from about 23 °C to about 130°C.
- Embodiment 34 The method according to any of Embodiments 1-33, wherein the average temperature of the thermoplastic is maintained at a temperature from about 90°C to about 130°C.
- Embodiment 35 The method according to any of Embodiments 1-34, wherein the average temperature of the thermoplastic is maintained at a temperature of about 90°C.
- Embodiment 36 The method according to any of Embodiments 1-35, wherein the average temperature of the thermoplastic is maintained at a temperature of about 120°C.
- Embodiment 37 The method according to any of Embodiments 1-36, wherein measuring the degree of discoloration of the thermoplastic comprises: illuminating the thermoplastic with white light, a portion of the white light being transmitted through the thermoplastic; and generating a transmission spectrum from the portion of the white light transmitted through the thermoplastic.
- Embodiment 38 The method according to any of Embodiments 1-36, wherein measuring the degree of discoloration of the thermoplastic comprises: illuminating the thermoplastic with white light, a portion of the white light being reflected from the thermoplastic; and generating a reflectance spectrum of the portion of the white light reflected from the thermoplastic.
- Embodiment 39 The method according to any of Embodiments 1-38, further comprising evaluating a degree of discoloration of the polycarbonate after the first period of time has elapsed.
- Embodiment 40 The method according to any of Embodiments 1-39, wherein the first period of time is about 100 hours in duration.
- Embodiment 41 The method according to any of Embodiments 1-40, further comprising cooling the thermoplastic.
- Embodiment 42 The method according to any of Embodiments 1-41, wherein the thermoplastic is transparent.
- Embodiment 43 The method according to any of Embodiments 1-41, wherein the thermoplastic is translucent.
- Embodiment 44 The method according to any of Embodiments 1-41, wherein the thermoplastic is opaque.
- the polycarbonate samples for each formulation comprised square plates approximately 30x30 mm and 1.5 mm thick.
- Each sample transparent polycarbonate formulation was illuminated with light having a peak intensity centered on 447 nm (measured radiometrically) at an irradiance of 50,000 W/m (calibration via a power meter). The illumination of the samples was performed in an oven within which the sample temperature (average of two samples) was maintained at a temperature of 120°C.
- Illumination was provided over a series of 6 (unequal) intervals for a total of 1,729 hours or until failure of the sample. Samples which experienced catastrophic failure (i.e., melting, charring) were removed from the oven between successive periods of illumination. At the end of each interval, the samples were allowed to coo! and their % transmittance ratio and degree of discoloration, as determined using the Yellowness Index, was measured using a
- the % transmittance ratio was calculated by measuring an initial % transmittance value for each sample before exposure of the samples and then measuring the % transmittance of each sample after each exposure interval and then calculating the ratio of the % transmittance after each exposure interval to the initial % transmittance.
- the % transmittance measurements were determined according to ASTM D 1003-00 (2000) using procedure A and CIE illuminant C and 2 degree observer on an X-Rite i7 spectrophotometer using an integrating sphere with 8 diffuse geometry, specular component included, UV included, 6mm small area view lens, and 25 mm large area view transmission port, with the percent transmittance value reported as Y (luminous tra smittance) taken from the CIE 1931 tristimulus values XYZ, The YI (yellowness index) was detennined according to ASTM D1925-95 (1995) CIE illuminant C and 2 degree observer on a X-Rite i7 spectrophotometer using an integrating sphere with
- sample 1 failing (melted) at 1,197 hours exposure
- sample 2 having a yellowness index of 2.14 and a % transmittance ratio of 98.86% at 1,729 hours exposure
- sample 3 having a yellowness index of 0.46 and a % transmittance ratio of 98.67 at 1,729 hours exposure
- sample 4 having a yellowness index of 0.19 and a % transmittance ratio of 98.82% at 1,729 hours exposure.
- testing using the method according to the invention was conducted on four different white opaque polymer formulations.
- the samples for each formulation comprised square plates approximately 30x30 mm and 1.5 mm thick.
- Each sample polymer formulation was illuminated with light having a peak intensity centered on 447 nm (measured radiometrically) at an irradiance of 50,000 W/m (calibration via a power meter).
- the illumination of the samples was performed in an oven within which the sample temperature (average of two samples) was maintained at a temperature of 90°C. Illumination was provided over a single interval for a total of 33 hours or until failure of the sample. Samples which experienced catastrophic failure (i.e., melting, charring) were removed from the oven between successive periods of illumination.
- YI yellowness index
- sample 1 a polycarbonate
- sample 2 a polycarbonate having a higher glass transition temperature than sample 1
- sample 3 a polyester having a yellowness index of 0.0
- sample 4 a glass filled polyester having a yellowness index of 34.33.
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