NZ702055A - Sunscreen compositions containing an ultraviolet radiation-absorbing polymer - Google Patents
Sunscreen compositions containing an ultraviolet radiation-absorbing polymerInfo
- Publication number
- NZ702055A NZ702055A NZ702055A NZ70205514A NZ702055A NZ 702055 A NZ702055 A NZ 702055A NZ 702055 A NZ702055 A NZ 702055A NZ 70205514 A NZ70205514 A NZ 70205514A NZ 702055 A NZ702055 A NZ 702055A
- Authority
- NZ
- New Zealand
- Prior art keywords
- polyglycerol
- absorbing
- chromophore
- polymer composition
- valley
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 114
- 229920000642 polymer Polymers 0.000 title claims abstract description 82
- 239000000516 sunscreening agent Substances 0.000 title description 36
- 230000000475 sunscreen Effects 0.000 title description 5
- 229920000223 polyglycerol Polymers 0.000 claims abstract description 115
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 79
- GPLRAVKSCUXZTP-UHFFFAOYSA-N 3-(2,3-dihydroxypropoxy)propane-1,2-diol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- 230000000295 complement Effects 0.000 claims abstract description 10
- 230000000699 topical Effects 0.000 claims description 13
- 239000000969 carrier Substances 0.000 claims description 6
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 7
- 230000000379 polymerizing Effects 0.000 abstract description 4
- 239000000543 intermediate Substances 0.000 description 29
- -1 oxypropylene groups Chemical group 0.000 description 27
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 16
- 230000002209 hydrophobic Effects 0.000 description 15
- 238000004128 high performance liquid chromatography Methods 0.000 description 14
- 239000004615 ingredient Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000002835 absorbance Methods 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 210000003491 Skin Anatomy 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000002537 cosmetic Substances 0.000 description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- KFJDQPJLANOOOB-UHFFFAOYSA-M 2H-benzotriazole-4-carboxylate Chemical compound [O-]C(=O)C1=CC=CC2=C1N=NN2 KFJDQPJLANOOOB-UHFFFAOYSA-M 0.000 description 5
- 238000000149 argon plasma sintering Methods 0.000 description 5
- 125000004432 carbon atoms Chemical group C* 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000002211 ultraviolet spectrum Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000003852 triazoles Chemical class 0.000 description 4
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-Aminobenzoic acid Chemical class NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 125000003282 alkyl amino group Chemical group 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 150000001565 benzotriazoles Chemical class 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000000132 electrospray ionisation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 3
- 238000000338 in vitro Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- ISDGWTZFJKFKMO-UHFFFAOYSA-N 2-phenyl-1,3-dioxane-4,6-dione Chemical compound O1C(=O)CC(=O)OC1C1=CC=CC=C1 ISDGWTZFJKFKMO-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- DSSYKIVIOFKYAU-UHFFFAOYSA-N Camphor Chemical compound C1CC2(C)C(=O)CC1C2(C)C DSSYKIVIOFKYAU-UHFFFAOYSA-N 0.000 description 2
- 206010015150 Erythema Diseases 0.000 description 2
- 210000004209 Hair Anatomy 0.000 description 2
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl methoxycinnamate Chemical class CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N Stearic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- HEAHZSUCFKFERC-AXPXABNXSA-N [(2Z)-2-[[4-[(Z)-[7,7-dimethyl-3-oxo-4-(sulfomethyl)-2-bicyclo[2.2.1]heptanylidene]methyl]phenyl]methylidene]-7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl]methanesulfonic acid Chemical compound CC1(C)C2CCC1(CS(O)(=O)=O)C(=O)\C2=C/C(C=C1)=CC=C1\C=C\1C(=O)C2(CS(O)(=O)=O)CCC/1C2(C)C HEAHZSUCFKFERC-AXPXABNXSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 125000004429 atoms Chemical group 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000003974 emollient agent Substances 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 231100000321 erythema Toxicity 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000003906 humectant Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- BSUNTQCMCCQSQH-UHFFFAOYSA-N triazine Chemical compound C1=CN=NN=C1.C1=CN=NN=C1 BSUNTQCMCCQSQH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- MUTZWJYYDYUTBC-UHFFFAOYSA-N 2-benzoyl-6-hydroxybenzoic acid Chemical class OC(=O)C1=C(O)C=CC=C1C(=O)C1=CC=CC=C1 MUTZWJYYDYUTBC-UHFFFAOYSA-N 0.000 description 1
- OIQXFRANQVWXJF-UHFFFAOYSA-N 2-benzylidene-4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical compound CC1(C)C2CCC1(C)C(=O)C2=CC1=CC=CC=C1 OIQXFRANQVWXJF-UHFFFAOYSA-N 0.000 description 1
- TYYHDKOVFSVWON-UHFFFAOYSA-N 2-butyl-2-methoxy-1,3-diphenylpropane-1,3-dione Chemical compound C=1C=CC=CC=1C(=O)C(OC)(CCCC)C(=O)C1=CC=CC=C1 TYYHDKOVFSVWON-UHFFFAOYSA-N 0.000 description 1
- JGUMTYWKIBJSTN-UHFFFAOYSA-N 2-ethylhexyl 4-[[4,6-bis[4-(2-ethylhexoxycarbonyl)anilino]-1,3,5-triazin-2-yl]amino]benzoate Chemical compound C1=CC(C(=O)OCC(CC)CCCC)=CC=C1NC1=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=N1 JGUMTYWKIBJSTN-UHFFFAOYSA-N 0.000 description 1
- KIJLLVHZHRVDLH-UHFFFAOYSA-N 2-hydroxy-6-(3-oxo-3-phenylprop-1-enyl)benzoic acid Chemical class OC(=O)C1=C(O)C=CC=C1C=CC(=O)C1=CC=CC=C1 KIJLLVHZHRVDLH-UHFFFAOYSA-N 0.000 description 1
- UVCJGUGAGLDPAA-UHFFFAOYSA-N 2-phenyl-3H-benzimidazole-5-sulfonic acid Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 description 1
- 229940000641 4-Aminobenzoic Acid Drugs 0.000 description 1
- HEOCBCNFKCOKBX-SDNWHVSQSA-N 4-Methylbenzylidene camphor Chemical compound C1=CC(C)=CC=C1\C=C/1C(=O)C2(C)CCC\1C2(C)C HEOCBCNFKCOKBX-SDNWHVSQSA-N 0.000 description 1
- AICYRZRYRROYFV-UHFFFAOYSA-N 4-[1-(2H-benzotriazol-4-yloxy)-2,3,4,5-tetramethyl-6-pent-1-en-2-ylcyclohexa-2,4-dien-1-yl]-2H-benzotriazole Chemical compound CCCC(=C)C1C(C)=C(C)C(C)=C(C)C1(C=1C=2N=NNC=2C=CC=1)OC1=CC=CC2=C1N=NN2 AICYRZRYRROYFV-UHFFFAOYSA-N 0.000 description 1
- STYQHICBPYRHQK-UHFFFAOYSA-N 4-bromobenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=C(Br)C=C1 STYQHICBPYRHQK-UHFFFAOYSA-N 0.000 description 1
- JKEWHJRARLJYAN-UHFFFAOYSA-N 4-hydroxy-2-oxochromene-3-carboxylic acid Chemical class C1=CC=C2OC(=O)C(C(=O)O)=C(O)C2=C1 JKEWHJRARLJYAN-UHFFFAOYSA-N 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- UBNYRXMKIIGMKK-RMKNXTFCSA-N Amiloxate Chemical compound COC1=CC=C(\C=C\C(=O)OCCC(C)C)C=C1 UBNYRXMKIIGMKK-RMKNXTFCSA-N 0.000 description 1
- RWZYAGGXGHYGMB-UHFFFAOYSA-N Anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N Benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- 241000195940 Bryophyta Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- NZZIMKJIVMHWJC-UHFFFAOYSA-N Dibenzoylmethane Chemical class C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 1
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- HUVYTMDMDZRHBN-UHFFFAOYSA-N Drometrizole trisiloxane Chemical compound C[Si](C)(C)O[Si](C)(O[Si](C)(C)C)CC(C)CC1=CC(C)=CC(N2N=C3C=CC=CC3=N2)=C1O HUVYTMDMDZRHBN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
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- XMIIGOLPHOKFCH-UHFFFAOYSA-N Phenylpropanoic acid Chemical group OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
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- UEVAMYPIMMOEFW-UHFFFAOYSA-N Trolamine salicylate Chemical compound OCCN(CCO)CCO.OC(=O)C1=CC=CC=C1O UEVAMYPIMMOEFW-UHFFFAOYSA-N 0.000 description 1
- 230000037338 UVA radiation Effects 0.000 description 1
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- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229960002709 amiloxate Drugs 0.000 description 1
- 230000003712 anti-aging Effects 0.000 description 1
- 229940058303 antinematodal Benzimidazole derivatives Drugs 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229960005193 avobenzone Drugs 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 238000004364 calculation method Methods 0.000 description 1
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- 239000006071 cream Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000004059 degradation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 229960000655 ensulizole Drugs 0.000 description 1
- 229960004697 enzacamene Drugs 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 238000005755 formation reaction Methods 0.000 description 1
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- 238000004156 green chemistry Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 229930005346 hydroxycinnamic acids Natural products 0.000 description 1
- 235000010359 hydroxycinnamic acids Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 239000004005 microsphere Substances 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- 235000011929 mousse Nutrition 0.000 description 1
- 125000004433 nitrogen atoms Chemical group N* 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000269 nucleophilic Effects 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229960001679 octinoxate Drugs 0.000 description 1
- 229960000601 octocrylene Drugs 0.000 description 1
- WCJLCOAEJIHPCW-UHFFFAOYSA-N octyl 2-hydroxybenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1O WCJLCOAEJIHPCW-UHFFFAOYSA-N 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- BARWIPMJPCRCTP-CLFAGFIQSA-N oleyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC BARWIPMJPCRCTP-CLFAGFIQSA-N 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229960001173 oxybenzone Drugs 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- VYMDGNCVAMGZFE-UHFFFAOYSA-N phenylbutazonum Chemical class O=C1C(CCCC)C(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 VYMDGNCVAMGZFE-UHFFFAOYSA-N 0.000 description 1
- 229920000844 poly(butylene succinate-co-adipate) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229940068886 polyethylene glycol 300 Drugs 0.000 description 1
- 229920002282 polysilicones-15 Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002335 preservative Effects 0.000 description 1
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- 230000002035 prolonged Effects 0.000 description 1
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- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
- 230000003595 spectral Effects 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 229960000368 sulisobenzone Drugs 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940030300 trolamine salicylate Drugs 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
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Abstract
Polymer compositions containing an ultraviolet radiation absorbing polyglycerol that has low fractions of diglycerol chromophore conjugates and that includes a UV-chromophore chemically bound thereto are provided, as well as processes to prepare such polymer compositions that includes preparing a polyglycerol intermediate by polymerizing glycerol; removing residual glycerol and low molecular weight fractions from the polyglycerol intermediate to form an enriched polyglycerol intermiedate having low fractions of diglycerol; and reacting the enriched polyglycerol intermediate with a UV-chromophore having a complementary functional group to form the polymer composition, and compositions using the ultraviolet radiation absorbing polyglycerol. lyglycerol intermediate by polymerizing glycerol; removing residual glycerol and low molecular weight fractions from the polyglycerol intermediate to form an enriched polyglycerol intermiedate having low fractions of diglycerol; and reacting the enriched polyglycerol intermediate with a UV-chromophore having a complementary functional group to form the polymer composition, and compositions using the ultraviolet radiation absorbing polyglycerol.
Description
SUNSCREEN COMPOSITIONS CONTAINING AN
ULTRAVIOLET RADIATION-ABSORBING POLYMER
FIELD OF THE INVENTION
The present invention relates to polymer compositions comprising UV-absorbing
polyglycerols.
BACKGROUND OF THE INVENTION
The prolonged exposure to ultraviolet (UV) radiation, such as from the sun, can lead
to the formation of light dermatoses and erythemas, as well as increase the risk of skin
cancers, such as melanoma, and accelerate skin aging, such as loss of skin elasticity and
wrinkling.
Numerous sunscreen compositions are commercially available with varying ability to
shield the body from ultraviolet light. However, numerous challenges still exist to provide
sunscreen compositions that provide strong UV radiation protection.
SUMMARY OF THE INVENTION
The present invention relates to polymer compositions including an ultraviolet
radiation absorbing polyglycerol. The ultraviolet radiation absorbing polyglycerol includes a
UV-chromophore chemically bound thereto. The polymer composition has low fractions of
diglycerol chromophore conjugates. The present invention further relates to processes for
making the ultraviolet radiation absorbing polyglycerol that includes preparing a polyglycerol
intermediate by reacting glycerol with a multivalent inorganic base; and reacting the
polyglycerol intermediate with a UV-chromophore having a complementary functional group
to form the polymer composition.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 is a chromatogram of a polymer composition of the present invention.
Figure 2 is a chromatogram of a comparative polymer composition.
DETAILED DESCRIPTION OF THE INVENTION
Unless defined otherwise, all technical and scientific terms used herein have the same
meaning as commonly understood by one of ordinary skill in the art to which the invention
belongs. As used herein, unless otherwise indicated, all hydrocarbon groups (e.g., alkyl,
alkenyl) groups may be straight or branched chain groups. As used herein, unless otherwise
indicated, the term “molecular weight” refers to weight average molecular weight, (Mw).
Unless defined otherwise, all concentrations refer to concentrations by weight of the
composition. Also, unless specifically defined otherwise, the term “essentially free of,” with
respect to a class of ingredients, refers to the particular ingredient(s) being present in a
concentration less than is necessary for the particularly ingredient to be effective to provide
the benefit or property for which it otherwise would be used, for example, about 1% or less,
or about 0.5% or less.
As used herein, “UV-absorbing” refers to a material or compound, e.g. a polymeric or
non-polymeric sunscreen agent or a chemical moiety, which absorbs radiation in some portion
of the ultraviolet spectrum (290nm-400nm), such as one having an extinction coefficient of at
-1 -1
least about 1000 mol cm , for at least one wavelength within the above-defined ultraviolet
spectrum. SPF values disclosed and claimed herein are determined using the in-vitro method
described herein below.
UV-ABSORBING POLYGLYCEROL
Embodiments of the invention relate to compositions including an ultraviolet radiation
absorbing polyglycerol, (i.e., “UV-absorbing polyglycerol”). By UV-absorbing polyglycerol,
it is meant a polyglycerol that absorbs radiation in some portion of the ultraviolet spectrum
(wavelengths between 290 and 400 nm). The UV-absorbing polyglycerol has a weight
average molecular weight (M ) which may be suitable for reducing or preventing the
chromophore from absorbing through the skin. According to one embodiment, a suitable
molecular weight for the UV-absorbing polyglycerol is M greater than 500. In one
embodiment, M is in the range of about 500 to about 50,000. In another embodiment, M is
in the range of about 500 to about 5,000. In another embodiment, the M is in the range of
about 1,000 to about 20,000, such as from about 1,000 to about 10,000.
Described herein is a composition including a UV-absorbing polyglycerol. As one
skilled in the art will recognize, “polyglycerol” indicates that the UV-absorbing polymer
includes a plurality of glyceryl repeat units covalently bonded to each other. The “backbone”
of the UV-absorbing polyglycerol refers to the longest continuous sequence of covalently
bonded glyceryl repeat units. Other smaller groups of covalently bonded atoms are
considered pendant groups that branch from the backbone.
By “glyceryl repeat units” (also referred to herein as “glyceryl remnant units”) it is
meant glycerol units excluding nucleophilic groups such as hydroxyl groups. Glyceryl
remnant units include ether functional groups, and generally may be represented as C H O for
linear and dendritic remnants (Rokicki et al. Green Chemistry., 2005, 7, 52). Suitable
glyceryl remnant units include dehydrated forms (i.e. one mole of water removed) of the
following glyceryl units: linear-1,4 (L ) glyceryl units; linear-1,3 (L ) glyceryl repeat units;
1,4 1,3
dendritic (D) glyceryl units; terminal-1,2 (T ) units; and terminal-1,3 (T ) units. Examples
1,2 1,3
of linear glyceryl remnant units and terminal units are shown below (to the right side of the
arrows). The corresponding glyceryl unit before dehydration (shown to the left side of
arrows; includes hydroxyls) are shown as well:
linear-1,4 (L ) glyceryl repeat units
linear-1,3 (L ) glyceryl repeat units
terminal-1,2 (T ) units
and terminal-1,3 (T ) units
Those skilled in the art of polymer chemistry will recognize that a polyglycerol, like
any typical polymer, is comprised of repeating units and end groups. In the simple case of a
polymer formed by condensation of monomer units (elimination of water during
polymerization), the end groups are comprised of the parent molecule, while the repeating
unit is derived from the parent monomer minus a water molecule. Such is the case for
polyglycerols, which can be synthesized by using the monomer glycerol.
This is further illustrated in the Structure I below, where repeating unit isomers have
been demarcated by parentheses (7 total glyceryl repeat units) and the terminal glyceryl
remnant demarcated by brackets (1 terminal glyceryl remnant), yielding a total degree of
polymerization (DP) of 8. The "Z" in Structure I is selected from a UV-chromophore, a
hydrophobic moiety, or an unreacted hydroxyl group.
O H Z
H O O O
O O O
Z Z O
E n d G r o u p
E n d G r o u p
H O O
FORMULA I. UV-ABSORBING POLYGLYCEROL
As described above, the polyglycerol may include one or more hydrophobic moieties.
Suitable hydrophobic moieties include, for example, nonpolar moieties that contain at least
one of the following: (a) a carbon-carbon chain of at least six carbons in which none of the
six carbons is a carbonyl carbon or has a hydrophilic moiety bonded directly to it; (b) three or
more alkyl siloxy groups (-[Si(R) -O]-); and/or (c) three or more oxypropylene groups in
sequence. A hydrophobic moiety may be, or include, linear, cyclic, aromatic, saturated or
unsaturated groups. Preferred hydrophobic moieties include 6 or more carbon atoms, more
preferably from 8 to 30 carbon atoms, even more preferably from 10 to 26 carbon atoms, and
most preferably from 12 to 24 carbon atoms. Examples of hydrophobic moieties include
linear or branched, saturated or unsaturated alkyl moieties, e.g. linear or branched, saturated
or unsaturated C -C alkyl, such as decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl
8 30
(myristyl), pentadecyl, hexadecyl (cetyl, palmityl), heptadecyl, heptadecenyl, heptadecenyl,
hepta-8,11-decenyl, octadecyl (stearyl), nonadecyl, eicosanyl, henicosenyl, henicosanyl,
docosanyl (behenyl), and the like as well as benzyl. Certain preferred hydrophobic moieties
include heptadecyl, heptadecenyl, heptadecenyl, hepta-8,11-decenyl and the like. Other
examples of hydrophobic moieties include groups such as poly(oxypropylene),
poly(oxybutylene), poly(dimethylsiloxane), and fluorinated hydrocarbon groups containing a
carbon chain of at least six carbons in which none of the six carbons has a hydrophilic moiety
bonded directly to it, and the like.
According to certain embodiments, polymer compositions of the present invention
include low fractions of diglycerol chromophore conjugates. By “diglycerol chromophore
conjugates,” it is meant polyglycerols having two glyceryl repeat units and at least one
chemically-bound UV-chromophore. An example structure is shown below in FORMULA II
FORMULA II
By “low fractions” of diglycerol chromophore conjugates, it is meant that that the
valley-to-valley peak area of peaks assignable to diglycerol chromophore conjugates in the
ultraviolet radiation absorbing polyglycerol comprises about 1 percent or less of the total
valley-to-valley peak area of all peaks in the spectrogram, i.e. “total peak area”, such as about
0.5 percent or less of the total peak area, such as about 0.2 percent or less of the total peak
area, as determined by chromatogram analysis, as set forth in the Examples below.
As one skilled in the art will readily recognize, one particularly suitable method for
generating a chromatogram for determining the relative presence of chemical structures in a
polymer composition involves the use of high performance liquid chromatography (HPLC),
ultraviolet/visible (UV-VIS) and mass spectrometry (MS). For example, the polymer
composition may be tested for component analysis by separating components using HPLC.
Detection is performed using ultraviolet/visible (UV-VIS) and mass spectrometry (MS) to
generate a chromatogram of peaks at particular retention times, which peaks are assigned to
individual components. According to certain embodiments of the invention, such analysis
reveals no peak assignable to diglycerol chromophore conjugates. According to certain other
embodiments, if such a peak exists, As one skilled in the art will readily appreciate, total peak
area can be ascertained by connecting adjacent minima of points on the chromatogram and
calculating (integrating) area under the curve for each of the various peaks. A specific
suitable HPLC method for assessing the presence of diglycerol conjugates is provided below.
Polyglycerols described herein can be obtained through various synthetic routes. One
particularly suitable route includes preparing a polyglycerol intermediate by polymerizing
glycerol, such as by combining glycerol and suitable reactant such as an inorganic base
(alkali) into a reactor and applying vacuum, agitation and heat in order to facilitate the
polymerization of glycerol. By utilizing this method, glycerol is polymerized in a controlled
fashion which tends to produce high polyglycerol intermediates with high linearity (less
cyclic). According to one particular embodiment, the reactant is a multivalent inorganic base,
such as a calcium-containing compound, such as calcium hydroxide. The temperature of the
reactor may be maintained, for example between 200ºC and 240ºC, such as 220ºC and 240ºC.
Suitable pressures may be from about 10mm Hg to about 400mm Hg, such as from about
100mm Hg to about 400mm Hg, such as about 150 mm Hg. Suitable molar ratios of glycerol
to calcium-containing compound range from about 1:0.0002 to about 1:0.005.
According to certain embodiments, the polyglycerol intermediate is reacted with a
hydrophobic reactant. Suitable hydrophobic reactants are those that are capable of displacing
hydroxyl groups on the polyglycerol intermediate and covalently bonding thereto in order to
ultimately provide a hydrophobic moiety (described above) bound to the UV-absorbing
polyglycerol. As one skilled in the art will readily appreciate, suitable examples of
hydrophobic reactants include linear or branched, saturated or unsaturated C -C fatty acids,
8 30
capable of reacting with hydroxyls on the polyglycerol intermediate and attaching to the
polyglycerol via an ester linkage, C -C isocyanates capable of reacting with hydroxyls via a
8 30
urethane linkage. Other suitable hydrophobic reactants include C -C epoxides, C -C
8 30 8 30
halohydrins, C -C alkyl halides, among other hydrophobic reactants capable of
8 30
condensation reactions with pendant hydroxyls on the polgylcerol intermediate. In this
embodiment, a hydrophobically-modified polyglycerol intermediate is formed.
According to certain embodiments, the polyglycerol intermediate (or hydrophobically-
modified polyglycerol intermediate) is enriched, i.e. residual glycerol and low molecular
weight (low DP) fractions of polyglycerol are removed from the polyglycerol intermediate to
form an enriched polyglycerol intermiedate. Residual glycerol may be removed, for example,
by heating and applying a vacuum. Suitable conditions for removing unreacted glycerol may
be a temperature of about 200ºC and pressure of about 4mm Hg. Additional glycerol may be
removed by introducing steam through the bottom of the reactor
One particularly suitable method of removing glycerol as well as low DP components
such as diglycerol includes applying heat and vacuum to the polyglycerol intermediate while
the polyglycerol intermediate is drawn into a thin film. This so-called “wiped film
evaporation” includes providing the polyglycerol intermediate to a chamber having a heated
surface, applying vacuum, spreading thin films of the polyglycerol intermediate across the
heated surface to selectively evaporate low molecular weight fractions of the polyglycerol
intermediate. Spreading of the polyglycerol intermediate may be performed mechanically,
such as via flexible blades that rotate about an axis and within the chamber, drawing the fluid
polyglycerol intermediate into a film and facilitating evaporation and removal of fractions
that are desirably removed, to form an enriched polyglycerol intermediate. Temperatures may
be held at about 260ºC and pressures at about 10 to 50 millitorr.
Suitable UV-chromophores that may be chemically bound in UV-absorbing
polyglycerols of the present invention include UV-absorbing triazoles (a moiety containing a
five-membered heterocyclic ring with two carbon and three nitrogen atoms), such as
benzotriazoles. In another embodiment, the UV-absorbing chromophore of Formulas I and II
includes a pendant UV-absorbing triazine (a six membered heterocycle containing three
nitrogen and three carbon atoms). Suitable UV-chromophores include those that have
absorbance of UVA radiation. Other suitable UV-chromophores are those which have
absorbance in the UVB region. In one embodiment, the UV-chromophore absorbs in both the
UVA and UVB region. In one embodiment, when the UV-absorbing polyglycerol is cast into
a film, it is possible to generate a molar extinction coefficient measured for at least one
-1 -1
wavelength in this wavelength range of at least about 1000 mol cm , preferably at least
-1 -1 -1 -1
about 2000 mol cm , more preferably at least about 4000 mol cm . In one embodiment,
the molar extinction coefficient among at least 40% of the wavelengths in this portion of the
-1 -1
spectrum is at least about 1000 mol cm . Examples of UV-chromophores that are UVA
absorbing include triazoles such as benzotriazoles, such as hydroxyphenyl-benzotriazoles;
camphors such as benzylidene camphor and its derivatives (such as terephthalylidene
dicamphor sulfonic acid); dibenzoylmethanes and their derivatives.
In one embodiment, the UV-chromophore is a benzotriazole providing both
photostability and strong UVA absorbance with a structure represented in FORMULA III.
FORMULA III. BENZOTRIAZOLE UV-ABSORBING CHROMOPHORE
wherein each R is independently selected from the group consisting of hydrogen, C -C
14 1 20
alkyl, alkoxy, acyl, alkyloxy, alkylamino, and halogen; R is independently selected from the
group consisting of hydrogen, C -C alkyl, alkoxy, acyl, alkyloxy, and alkylamino, R is
1 20 21
selected from C -C alkyl, alkoxy, acyl, alkyloxy, and alkylamino. Either of the R or R
1 20 15 21
groups may include the remnants of functional groups after reaction between the UV-
chromophore and the enriched polyglycerol intermediate. Compounds resembling the
structure in FORMULA are described in U.S. Pat. No. 5,869,030, and include, but are not
limited to, methylene bis-benzotriazolyl tetramethylbutylphenol (a compound sold under the
trade name TINSORB M by BASF Corporation, Wyandotte, Michigan). In one embodiment,
the UV-absorbing triazole is derived from a transesterification product of 3-(3-(2H-
benzo[d][1,2,3]triazolyl)(tert-butyl)hydroxyphenyl) propanoic acid with polyethylene
glycol 300, commercially available as TINUVIN 213, also available from BASF. In another
embodiment, the UV-absorbing triazole is Benzenepropanoic acid, 3-(2H-benzotriazolyl)-
-(1, 1-dimethylethyl)hydroxy-, C - -branched and linear alkyl esters, commercially
available as TINUVIN 99, also available from BASF. In another embodiment, the UV-
absorbing group contains a triazine moiety. An exemplary triazine is 6-octyl(4-(4,6-
di([1,1'-biphenyl]yl)-1,3,5-triazinyl)hydroxyphenoxy) propanoate (a compound sold
under the trade name TINUVIN 479 by BASF Corporation, Wyandotte, Michigan).
In another embodiment, the UV-chromophore is a UVB-absorbing moiety. By UVB-
absorbing chromophore it is meant that the UV-chromophore has absorbance in the UVB
portion (290 to 320 nm) of the ultraviolet spectrum. In one embodiment, the criteria for
consideration as a UVB-absorbing chromophore is similar to those described above for an
UVA-absorbing chromophore, except that the wavelength range is 290 nm to 320 nm.
Examples of suitable UVB-absorbing chromophores include 4-aminobenzoic acid and alkane
esters thereof; anthranilic acid and alkane esters thereof; salicylic acid and alkane esters
thereof; hydroxycinnamic acid alkane esters thereof; dihydroxy-, dicarboxy-, and
hydroxycarboxybenzophenones and alkane ester or acid halide derivatives thereof;
dihydroxy-, dicarboxy-, and hydroxycarboxychalcones and alkane ester or acid halide
derivatives thereof; dihydroxy-, dicarboxy-, and hydroxycarboxycoumarins and alkane ester
or acid halide derivatives thereof; benzalmalonate (benzylidene malonate); benzimidazole
derivatives (such as phenyl benzilimazole sulfonic acid, PBSA), benzoxazole derivatives, and
other suitably functionalized species capable of being covalently bonded within the polymer
chain. In another embodiment, the UV-absorbing polyglycerol includes more than one UV-
chromophore, or more than one chemical class of UV-chromophore.
According to certain embodiments of the invention, in order to provide a chemically
bound UV-chromophore on UV-absorbing polyglycerols present in polymer compositions of
the present invention, a “post-polymerization attachment” technique may be employed.
Unreacted, pendant hydroxyl groups present in the polyglycerol intermediate are reacted with
a UV-chromophore containing a complementary functional group to obtain a UV-absorbing
polyglycerol. Suitable complementary functional groups on UV-chromophore include
carboxylates, isocyanates, epoxides, esters, alkyl esters, acid halides, and the like. One
example of a UV-chromophore having complementary functional groups is a benzotriazole
carboxylate UV-chromophore, 3-(3-(2H-benzo[d][1,2,3]triazolyl)(tert-butyl)
hydroxyphenyl) propanoic acid, shown below in FORMULA IV.
FORMULA IV
In this embodiment, the pendant hydroxyls on the enriched polyglycerol intermediate
react via condensation with the complementary carboxylate functional group on the UV-
chromophore. Benzotriazoles having carboxylate or other complementary functional groups
may be prepared using methods known to those skilled in the art, such as those described in
published U.S. patent application 2012/0058974, “Composition Comprising Pesticide and
Benzotriazole UV Absorbers,” which is herein incorporated by reference in its entirety.
Polymer compositions formed via these methods are accordingly the reaction product
of enriched polyglycerol intermediate or, alternatively, a hydrophobically modified
polyglyerol, such as a polyglycerol ester, and a UV-chromophore having a functional group
suitable for covalent attachment to the polyglycerol intermediate.
According to one specific embodiment, a polyglycerol intermediate is formed by
polymerizing glycerol by reacting glycerol with calcium hydroxide. The temperature of the
reactor is maintained between 200ºC and 240ºC, and pressure is maintained at about 400mm
Hg and using a molar ratio of glycerol to calcium hydroxide from about 1:0.0002 to about
1:0.005. Residual glycerol and low molecular weight polyglycerols are removed using a
wiped film evaporator having a barrel temperature of about 260ºC and pressures at about 10
to 50 millitorr, thereby forming an enriched polyglycerol intermediate. The enriched
polyglycerol intermediate is optionally esterified with stearic acid at elevated temperature
(about 250ºC) for several hours until clear, to form a hydrophobically-modified polyglycerol
intermediate. Excess hydroxide is neutralized with phosphoric acid.
A benzotriazole carboxylate is prepared by adding, for example, the polyethylene
glycol ester of 3-[3-(2H-1,2,3-benzotriazolyl)tert-butylhydroxyphenyl]propanoate (a
chromophore sold under the trade name TINUVIN 213 by BASF Corporation, Wyandotte,
Michigan). 81.0 g is added to a 2 L round bottom flask containing a magnetic stir bar.
Ethanol (600 mL) is added to the flask by funnel, and the mixture is stirred until
homogeneous. Sodium hydroxide (NaOH, 30.8 g) is dissolved in H O (400 mL); the basic
solution is transferred into an addition funnel above the 2L flask. The NaOH solution is
added slowly to the stirred mixture. When addition is complete, the mixture is stirred
overnight at room temperature. The solution is concentrated by rotary evaporation to remove
most of the ethanol. The resulting orange oil is diluted to 1400 mL with H O. The mixture is
stirred mechanically and acidified to ~ pH 1 by addition of 1 M aq. HCl (~ 700 mL). The
resulting white precipitate is filtered and pressed to remove water, then recrystallized from
ethanol. The supernatant is removed and concentrated by rotary evaporation; a second crop
of material is isolated as a white, amorphous solid. The two crops are combined and dried in
a vacuum oven overnight to form a benzotriazole carboxylate.
The enriched, hydrophobically-modified polyglycerol is reacted with the benzotriazole
carboxylate (8.8 g, 23.8 mmol) by transferring into a 2-neck 100 mL round bottom flask
containing a magnetic stir bar. The flask is fitted with a nitrogen inlet adapter and distillation
adapter with 100 mL receiving flask. The apparatus is placed under vacuum for one hour,
then backfilled with nitrogen. The distillation head is removed, and tin (II) ethyl hexanoate
(50 µL) is added to the reaction flask by syringe under nitrogen flow. The apparatus is
reassembled, then purged under vacuum and backfilled with nitrogen 3 times. The reaction
flask is immersed in an oil bath that was warmed to 180 °C with constant flow of nitrogen
into the 2-neck flask through the distillation adapter and out of the vacuum adapter to room
atmosphere. The reaction is stirred for three hours and then cooled to room temperature
under nitrogen flow, affording the product, a polymer composition including UV-absorbing
polyglycerol, as a yellow solid.
As one skilled in the art will recognize, the UV-absorbing polyglycerols that are
useful in topical compositions of the present invention are prepared via polymer synthesis.
Synthesis of the UV-absorbing polyglycerol generally results in a reaction product, hereinafter
referred to as a “polymer composition”, that is a mixture of various molecular weights of UV-
absorbing polyglycerols. Despite the removal/reduction of glycerol and low-molecular
glycerol conjugates, the polymer composition may further include (apart from the UV-
absorbing polyglycerol composition) a small amount of unbound, i.e. unconjugated, material,
e.g., glycerol, chromophore or hydrophobic moieties that are not covalently bound to the
polyglycerol backbone.
According to certain embodiments, the polymer composition to be incorporated into
topical compositions of the present invention comprises about 90% or more of the UV-
absorbing polyglycerol that comprises a UV-chromophore chemically bound thereto.
According to certain other embodiments, the polymer composition comprises about 95% or
more of the UV-absorbing polyglycerol that comprises a UV-chromophore chemically bound
thereto. According to certain other embodiments, the polymer composition comprises about
98% or more of the linear UV-absorbing polyglycerol having a chromophore chemically
bound thereto, such as about 99% or more.
The polymer compositions described herein are useful in applications where UV
absorption is desired. For example, the polymer composition may be useful for combining
with a suitable cosmetically acceptable carrier for cosmetic applications or combining the
polymer composition with other materials to reduce UV degradation of the materials ( i.e.,
melt blending the material with the polymer composition or coating the material with the UV-
absorbing polymer). The incorporation of UV-absorbing polyglycerols into such
compositions of the present invention may provide enhanced SPF (primarily UVB
absorbance), enhanced PFA (primarily UVA absorbance) or enhancement of both. The
cosmetically-acceptable topical carrier is suitable for topical application to human skin and
may include for example, one or more of vehicles such as water, ethanol, isopropanol,
emollients, humectants, and/or one or more of surfactants/emulsifiers, fragrances,
preservatives, water-proofing polymers, and similar ingredients commonly used in cosmetic
formulations. As such, the polymer composition may be formulated using ingredients known
in the art into a spray, lotion, gel, stick or other product forms. Similarly, according to certain
embodiments, one may protect human skin from UV radiation by topically applying a
composition comprising the polymer composition containing the UV-absorbing polyglycerol.
According to certain embodiments, the sunscreen agent present in topical
compositions of the present invention may consist of, or consists essentially of, the UV-
absorbing polyglycerol having the chromophore chemically bound thereto, as defined herein.
According to certain other embodiments, the sunscreen agent may include additional UV-
absorbing polymers, other than those UV-absorbing polyglycerols, as defined herein, and/or
non-UV-absorbing, light-scattering particles. Additional UV-absorbing polymers are
molecules that can be represented as having one or more structural units that repeat
periodically, e.g., at least twice, to generate the molecule, and may be UV-absorbing
polyglycerols, other than those as defined and claimed in this specification. In certain
embodiments, the compositions may be substantially free of UV-absorbing polymers other
than the UV-absorbing polyglycerols. By “substantially free of UV-absorbing polymers other
than the UV-absorbing polyglycerols”, it is meant that the compositions do not contain UV-
absorbing polymers other than the UV-absorbing polyglycerols in an amount effective to
provide the compositions with an SPF of greater than 2 in the absence of the UV-absorbing
polyglycerol and non-polymeric UV-absorbing sunscreen agents. In yet other embodiments,
the compositions may be substantially free of both UV-absorbing polymers other than the
UV-absorbing polyglycerols and non-polymeric UV-absorbing sunscreen agents, as described
below. For example, the compositions of the invention will contain about 1% or less, or about
0.5% or less, of such UV-absorbing polymers other than the UV-absorbing polyglycerols
and/or such non-polymeric absorbing UV-absorbing sunscreen agents.
Additional UV-absorbing polymers may have a molecular weight of greater than
about 1500. Examples of suitable additional UV-absorbing polymers include benzylidene
malonate silicone, including those described in US Patent 6,193,959, to Bernasconi et al. A
particularly suitable benzylidene malonate includes “Parsol SLX,” commercially available
from DSM (Royal DSM N.V.) of Heerlen, Netherlands. Other suitable additional UV-
absorbing polymers are disclosed in US 6, 962,692; US 6,899, 866; and/or US 6,800,274;
including hexanedioic acid, polymer with 2,2-dimethyl-1,3-propanediol,
3-[(2-cyanooxo-3,3-diphenylpropenyl)oxy]-2,2-dimethylpropyl 2-octyldodecyl ester;
sold under the trade name “POLYCRYLENE,” commercially available from the HallStar
Company of Chicago, Illinois. When utilized, such additional UV-absorbing polymers may be
used at concentrations of about 1% or more, for example about 3% or more.
Non-UV-absorbing, light-scattering particles do not absorb in the UV spectrum, but
may enhance SPF by scattering of the incident UV radiation. Examples of non-UV-
absorbing, light-scattering particles include solid particles having a dimension, e.g., average
diameter, from about 0.01 micron to about 10 microns. In certain embodiments, the non-UV-
absorbing, light-scattering particle is a hollow particle comprising, or consisting essentially
of, an organic polymer or a glass. Suitable organic polymers include acrylic polymers,
including acrylic/styrene copolymers, such as those known as SUNSPHERES, which are
commercially available from Dow Chemical of Midland, Michigan. Suitable glasses include
borosilicate glasses such as those described in published United States Patent Application
US20050036961A1, entitled, “AESTHETICALLY AND SPF IMPROVED UV-
SUNSCREENS COMPRISING GLASS MICROSPHERES”.
TOPICAL COMPOSITION
In one embodiment, a composition suitable for topical/cosmetic use for application to
the human body, e.g., keratinaceous surfaces such as the skin, hair, lips, or nails, and
especially the skin, is provided. The composition includes the polymer composition
comprising the UV-absorbing polyglycerols that comprise a UV-chromophore chemically
bound thereto.
As discussed above, the concentration of the UV-absorbing polyglycerol comprise a
UV-chromophore chemically bound thereto in the topical composition may be sufficient to
provide an SPF of about 10 or greater, particularly where the composition is free of, or
substantially free of, additional UV-absorbing polymers, i.e. UV-absorbing polymers other
than the UV-absorbing polyglycerols comprising a UV-chromophore chemically bound
thereto, or non-polymeric UV-absorbing sunscreen agents as described herein. Accordingly,
the concentration of the UV-absorbing polyglycerol may vary from about 5% to about 50%,
such as from about 7% to about 40%, such as from about 10% to about 30%, such as from
about 15% to about 30% of the composition. In certain embodiments, the concentration of
UV-absorbing polyglycerol is about 10% or more, such as about 15% or more, such about
% or more of the composition. According to certain embodiments where the sunscreen
agent consists essentially of the UV-absorbing polyglycerol, the concentration of the UV-
absorbing polyglycerol may be about 15% or more.
The concentration of non-UV-absorbing light scattering particles, if present, may be
about 1% or more, such as from about 1% to about 10%, such as from about 2% to about 5%.
In certain embodiments where the UV-sunscreen agent further includes a non-UV-absorbing
sunscreen agent in amounts as discussed above, compositions of the present invention may
have an SPF of about 20 or greater.
Compositions of the present invention, according to certain embodiments, may be
substantially free of non-polymeric UV-absorbing sunscreen agents. By “substantially free of
non-polymeric UV-absorbing sunscreen agents,” it is meant that, in this embodiment, the
compositions do not contain non-polymeric UV-absorbing sunscreen agents in an amount
effective to provide the compositions with an SPF of greater than 2 in the absence of the UV-
absorbing polyglycerol and UV-absorbing polymers other than the UV-absorbing
polyglycerols used in the present invention, as determined via the in vitro method described
herein below. For example, the compositions of the invention will contain about 1% or less,
or about 0.5% or less, of such non-polymeric UV-absorbing sunscreen agents. One example
of non-polymeric UV-absorbing sunscreen agents that the composition is substantially free of
typically may be characterized as “organic” (include predominantly or only atoms selected
from carbon, hydrogen, oxygen, and nitrogen) and having no definable repeat unit and
typically having molecular weights that are about 600 daltons or less, such as about 500
daltons or less, such as less than 400 daltons. Examples of such compounds, sometimes
referred to as “monomeric, organic UV-absorbers” include, but are not limited to:
methoxycinnamate derivatives such as octyl methoxycinnamate and isoamyl
methoxycinnamate; camphor derivatives such as 4-methyl benzylidene camphor, camphor
benzalkonium methosulfate, and terephthalylidene dicamphor sulfonic acid; salicylate
derivatives such as octyl salicylate, trolamine salicylate, and homosalate; sulfonic acid
derivatives such as phenylbenzimidazole sulfonic acid; benzone derivatives such as
dioxybenzone, sulisobenzone, and oxybenzone; benzoic acid derivatives such as
aminobenzoic acid and octyldimethyl para-amino benzoic acid; octocrylene and other β,β-
diphenylacrylates; dioctyl butamido triazone; octyl triazone; butyl methoxydibenzoyl
methane; drometrizole trisiloxane; and menthyl anthranilate.
Other non-polymeric UV-absorbing sunscreen agents that the composition may be
substantially free of may include ultraviolet-absorbing particles, such as certain inorganic
oxides, including titanium dioxide, zinc oxide, and certain other transition metal oxides.
Such ultraviolet screening particles are typically solid particles having a diameter from about
0.1 micron to about 10 microns.
The compositions of the present invention may be used for a variety of cosmetic uses,
especially for protection of the skin from UV radiation. The compositions, thus, may be
made into a wide variety of delivery forms. These forms include, but are not limited to,
suspensions, dispersions, solutions, or coatings on water soluble or water-insoluble substrates
(e.g., substrates such as organic or inorganic powders, fibers, or films). Suitable product
forms include lotions, creams, gels, sticks, sprays, ointments, mousses, and
compacts/powders. The composition may be employed for various end-uses, such as
recreation or daily-use sunscreens, moisturizers, cosmetics/make-up, cleansers/toners, anti-
aging products, or combinations thereof. The compositions of the present invention may be
prepared using methodology that is well known by an artisan of ordinary skill in the field of
cosmetics formulation.
TOPICAL CARRIER
The one or more UV-absorbing polymers in the composition may be combined with a
"cosmetically-acceptable topical carrier,” i.e., a carrier for topical use that is capable of
having the other ingredients dispersed or dissolved therein, and possessing acceptable
properties rendering it safe to use topically. As such, the composition may further include
any of various functional ingredients known in the field of cosmetic chemistry, for example,
emollients (including oils and waxes) as well as other ingredients commonly used in personal
care compositions, such as humectants, thickeners, opacifiers, fragrances, dyes, solvents for
the UV-absorbing polyglycerol, among other functional ingredients. Suitable examples of
solvents for the UV-absorbing polyglycerol include dicaprylyl carbonate available as CETIOL
CC from Cognis Corporation of Ambler, Pennsylvania. In order to provide pleasant
aesthetics, in certain embodiments of the invention, the composition is essentially free of
volatile solvents, and, in particular, C -C alcohols such as ethanol and isopropanol.
Furthermore, the composition may be essentially free of ingredients that would render
the composition unsuitable for topical use. As such, the composition may be essentially free
of solvents such as volatile solvents, and, in particular, free of volatile organic solvents such
as ketones, xylene, toluene, and the like.
Sun protection factor (SPF) may be tested using the following IN-VITRO SPF TEST
METHOD. The baseline transmission of a PMMA plate (substrate) without application of
any test materials applied thereto was measured. Test samples were prepared by providing a
sample of polymer. Blends may also be tested by this method. The polymer(s) can be tested
without any additional additives; with a solvent system, or as a part of a personal care
composition that may include solvent and/or additional ingredients.
Each sample is separately applied to a PMMA plate (available from Helioscience,
Marseille, France) using an application density of about 1.3 mg/cm2, rubbing into a uniform
thin layer with the operator’s finger, and allowing to dry. The samples are allowed to dry for
minutes before measurement of absorbance using calibrated Labsphere® UV-1000S UV
transmission analyzer or a Labsphere® UV-2000S UV transmission analyzer (Labsphere,
North Sutton, N.H., USA). The absorbance measures are used to calculate SPF and PFA
indices.
SPF and PFA may be calculated using methods known in the art – see equation (1)
below for calculation of SPF:
where:
E(λ) = Erythema action spectrum
I(λ) = Spectral irradiance received from the UV source
A0(λ) = Mean monochromatic absorbance of the test product layer before UV
exposure
dλ = Wavelength step (1 nm)
The compositions of the present invention may be prepared using mixing and
blending methodology that is well known by an artisan of ordinary skill. In one embodiment
of the invention, a method of making a composition of the present invention includes
preparing an oil phase by mixing at least the UV-absorbing polyglycerol with optional oil-
soluble or oil-miscible ingredients; and preparing a water phase, by mixing water and optional
water-soluble or water-miscible ingredients. The oil phase and the water phase may then be
mixed in a manner sufficient to homogeneously disperse the oil phase in the water phase such
that the water phase is continuous and the oil phase discontinuous.
The compositions of the present invention can be used by topically administering to a
mammal, e.g., by the direct laying on, wiping or spreading of the composition on the skin or
hair of a human.
The following HPLC TEST is used in the instant methods and in the following
Examples. In particular, as described above, the HPLC TEST METHOD is used to determine
whether the polymer composition includes diglycerol chromophore conjugates.
HPLC TEST:
The HPLC (HIGH PERFORMANCE LIQUID CHROMATOGRAPHY) TEST is
designed to determine the relative concentrations of various components in the polymer
composition. The components of the polymer composition are separated by high performance
liquid chromatography (HPLC) and detected using ultraviolet visible (UV) spectrometry and
mass spectrometry (MS) to generate a chromatogram where each of the chromatographic
peaks at specific retention time corresponds to an individual component within the polymer
composition. Higher peak response (HPLC-UV peak area in this document) indicates a
higher concentration of a particular component. The values of HPLC-UV peak area are
obtained through a valley-to-valley integration using a well-qualified data process software
(LC/MSD ChemStation, Rev. B.0403-SP1 (87), Agilent Technologies, Inc., 2850 Centerville
Road, Wilmington, DE 19808-1610, USA). The molecular weight of each of the components
is obtained using mass spectrometric detection. Mass spectrometry directly measures the
molecular weight of each of the components after ionization. The mass spectrometer is
calibrated using an Agilent ESI Tuning Mix (Part # G2421A) standard with known molecular
weight to ensure the accuracy of the instrumentation. The molecular weight information is
used to propose corresponding chemical structures.
As one skilled in the art will readily recognize, the presence of diglycerol
chromophore conjugates in the polymer composition can be determined by calculating the
molecular weight of the diglycerol conjugate from its chemical structure, and matching the
molecular weight with retention time. For example, for a polymer compostition that is
formed by reacting an enriched polyglycerol ester intermiedate with the benzotriazole
carboxylate UV-chromophore, 3-(3-(2H-benzo[d][1,2,3]triazolyl)(tert-butyl)
hydroxyphenyl) propanoic acid, the diglycerol conjugate shown in Formula II has a molecular
weight of 790.4.
The following examples are illustrative of the principles and practice of this
invention, although not limited thereto. Numerous additional embodiments within the scope
and spirit of the invention will become apparent to those skilled in the art once having the
benefit of this disclosure.
EXAMPLES
EXAMPLE I
Two polymer compositions comprising a UV-absorbing polyglycerol were analyzed
using the HPLC METHOD. Inventive Polymer Composition A was made using a controlled
process designed to provide low fractions of diglycerol chromophore conjugates, while
Comparative Polymer Composition B was made using a conventional process. For each of the
polymer compositions, 100 mg of polymer composition was dissolved in 20 ml of
tetrahydrofuran (THF) to a concentration of 5,000 ppm followed with 5 times dilution with
THF to a final concentration of 1,000 ppm. The solutions were analyzed according to the
HPLC TEST using an Agilent LC/MSD SL, ID# SK 1519 (Agilent technologies, Santa Clara,
California). An Agilent Zorbax Eclipse XDBC8 column (3.5 micron, 150x3mm ID, S/N:
USOX002084) was employed with mobile phase A (20mM ammonium acetate in water:
ACN (10:90) and mobile phase B (isopropanol: ethyl acetate: 100mM ammonium acetate
(50:50:2). Elution time, flow rate, and relative amounts of mobile phases are provided in
Table 1, below:
TABLE 1: HPLC TEST: MOBILE PHASES
Binary gradient Flow rate (mL/min) Mobile phase A (%) Mobile phase B (%)
elution: Time (min)
0.00 0.30 100.0 0.0
.00 0.30 90.0 10.0
40.00 0.30 60.0 40.0
80.00 0.30 30.0 70.0
90.00 0.30 5.0 95.0
95.00 0.30 5.0 95.0
100.00 0.30 100.0 0.0
110.00 0.30 100.0 0.0
UV detection was set at 305nm. Mass spectrometric detection was set for electrospray
Ionization (ESI), positive ion mode with a scan setting of 650-3,000 amu; fragmentor: 400;
fain: 1.0; and drying gas temp at 350°C.
The HPLC-UV peaks and their retention times (RT) are summarized in Table 2. Two
relative major peaks, peak #2 (RT 8.88 min) and peak #4 (RT 12.45 min), were observed in
Polymer Composition B, but not observed in Polymer Composition A.
The species observed from HPLC-UV (Figure 1) were analyzed with a mass
spectrometric detector as indicated. The results were summarized in Table 3.
Mass spectrometric analysis indicates that Polymer Composition A has no peaks
assignable to the lowest molecular weight glycerol conjugates, specifically diglycerol
conjugates (i.e., structures recorded as “(G2-H2O)_T2”) correlating to retention times (RT)
8.88 and 12.45 minutes. In contrast, Polymer Composition B has 4.93% (RT 8.88) and
.81% (RT 12.45), respectively, for a combined peak area of 10.74% for the respective
retention times (RT 8.88 and RT 12.45). This indicates a surprising reduction in the percent
of diglycerol conjugates present in Polymer Composition A, as compared with Polymer
Composition B.
TABLE 2: HPLC TEST: UV ANALYSIS
PEAK Retention Time % OF TOTAL % OF TOTAL
NUMBER (min) PEAK AREA PEAK AREA
Polymer Polymer
Composition A Composition B
1 6.72 NA 0.54
2 8.88 4.93 NA
3 9.56 NA 0.78
4 12.45 5.81 NA
13.96 NA 2.20
6 18.02 NA 1.94
7 19.75 NA 0.72
8 21.06 3.76 2.81
9 23.60 1.07 4.37
26.19 3.73 2.48
11 28.52 1.66 2.65
12 31.71 NA 6.24
13 34.15 1.75 1.31
14 36.64 4.68 14.84
38.75 2.34 2.24
16 40.91 5.65 5.34
17 42.67 0.70 4.05
18 43.91 1.13 2.11
19 46.12 5.07 7.87
46.83 NA 6.36
21 47.83 1.51 NA
22 49.93 6.82 9.17
23 51.38 1.54 NA
24 53.32 4.16 1.67
54.63 2.95 2.94
26 56.76 5.87 4.39
27 58.98 5.42 2.40
28 60.06 NA 0.54
29 61.39 2.95 3.23
62.23 3.79 NA
31 64.26 4.73 2.55
32 66.68 5.07 1.95
33 69.02 2.91 1.36
34 70.65 3.66 0.96
72.48 0.65 NA
36 73.93 2.07 NA
37 75.19 0.57 NA
38 76.61 1.38 NA
39 78.71 0.67 NA
TABLE 3: HPLC TEST: MASS SPECTROMETRY (MS) ANALYSIS
Peak # RT (min) MW Nominal Nominal Observed Observed Proposed
Ions Ions Ions Ions Structure
(M+Na+) (M+2Na+) (M+Na+) (M+2Na+)
1 6.72 864.4 887.4 887.3 (G3-
H2O)_T2
2 8.88 790.4 813.4 813.2 (G2-
H2O)_T2
3 9.56 864.4 887.4 887.3 (G3-
H2O)_T2
4 12.45 790.4 813.4 813.2 (G2-
H2O)_T2
13.96 1204.7 1227.7 1227.8 C18-(G4-
H2O)_T2
6 18.02 1130.7 1153.7 1153.3 C18-(G3-
H2O)_T2
7 19.75 1130.7 1153.7 1153.3 C18-(G3-
H2O)_T2
8 21.06 1186.7 1209.7 1209.3 C18-(G4-
2H2O)_T2
9 23.60 1130.7 1153.7 1153.3 C18-(G3-
H2O)_T2
26.19 1186.7 1209.7 1209.3 C18-(G4-
2H2O)_T2
11 28.52 1599.9 1622.9 1622.4 C18-(G5-
H2O)_T3
12 31.71 1525.9 1548.9 1548.4 C18-(G4-
H2O)_T3
13 34.15 1599.9 1622.9 1622.4 C18-(G5-
H2O)_T3
14 36.64 1525.9 1548.9 1548.4 C18-(G4-
H2O)_T3
38.75 1581.9 1604.9 1604.4 C18-(G5-
2H2O)_T3
16 40.91 1451.8 1474.8 1474.4 C18-(G3-
H2O)_T3
17 42.67 1921.0 1944.0 1943.6 C18-(G5-
H2O)_T4
18 43.91 1995.1 2018.1 2017.6 C18-(G6-
H2O)_T4
19 46.12 1847.0 1870.0 1869.5 C18-(G4-
H2O)_T4
46.83 1921.0 1944.0 1943.5 C18-(G5-
H2O)_T4
21 47.83 1977.1 2000.1 1999.6 C18-(G6-
2H2O)_T4
22 49.93 1847.0 1870.0 1869.5 C18-(G4-
H2O)_T4
23 51.38 2372.2 2395.2 2394.6 C18-(G7-
2H2O)_T5
24 53.32 2242.2 2265.2 2264.6 C18-(G5-
H2O)_T5
54.63 2316.2 2339.2 2338.6 C18-(G6-
H2O)_T5
26 56.76 2242.2 2265.2 2264.6 C18-(G5-
H2O)_T5
27 58.98 2637.4 2660.4 2659.8 C18-(G6-
H2O)_T6
28 60.06 2711.4 1378.7 1378.8 C18-(G7-
H2O)_T6
29 61.39 2767.4 1406.7 1406.6 C18-(G8-
2H2O)_T6
62.23 3162.6 1604.3 1603.9 C18-(G9-
2H2O)_T7
31 64.26 3032.5 1539.3 1538.9 C18-(G7-
H2O)_T7
32 66.68 NA 2209.8 NA
33 69.02 2711.4 1378.7 1378.8 C18-(G7-
H2O)_T6
34 70.65 3427.7 1736.9 1736.4 C18-(G8-
H2O)_T8
72.48 3106.6 1576.3 1576.4 C18-(G8-
H2O)_T7
36 73.93 3822.9 1934.5 1933.9 C18-(G9-
H2O)_T9
37 75.19 NA NA
38 76.61 NA NA
39 78.71 NA NA
40 79.54 NA NA
It is understood that while the invention has been described in conjunction with the
detailed description thereof, that the foregoing description is intended to illustrate and not
limit the scope of the invention.
Claims (6)
1. A polymer composition comprising an ultraviolet radiation absorbing polyglycerol comprising a UV-chromophore chemically bound thereto, wherein a valley-to-valley peak area of chromatogram peaks assignable to diglycerol chromophore conjugates in said ultraviolet radiation absorbing polyglycerol comprises about 1 percent or less of a total valley-to-valley peak area of all chromatogram peaks.
2. The polymer composition of claim 1, wherein said valley-to-valley peak area of said chromatogram peaks assignable to said diglycerol chromophore conjugates is about 0.5 percent or less of said total peak area of all of said chromatogram peaks.
3. The polymer composition of claim 1, wherein said valley-to-valley peak area of said chromatogram peaks assignable to said diglycerol chromophore conjugates is about 0.2 percent or less of said total peak area of all of said chromatogram peaks.
4. A method of forming a polymer composition comprising an ultraviolet radiation absorbing polyglycerol, the method comprising: preparing a polyglycerol intermediate by reacting glycerol with a multivalent inorganic base; and reacting said polyglycerol intermediate with a UV-chromophore having a complementary functional group to form said polymer composition.
5. The method of claim 4, further comprising removing residual glycerol and low molecular weight fractions from said polyglycerol intermediate to form an enriched polyglycerol intermiedate, and reacting said enriched polyglycerol intermiedate with said UV- chromophore having a complementary functional group to form said polymer composition.
6. A composition comprising: a polymer composition comprising an ultraviolet radiation absorbing polyglycerol comprising a UV-chromophore chemically bound thereto, wherein a valley-to-valley peak area of chromatogram peaks assignable to diglycerol chromophore conjugates in said ultraviolet radiation absorbing polyglycerol comprises about 1 percent or less of a total valley-to-valley peak area of all chromatogram peaks; and a cosmetically-acceptable topical carrier.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US14/132,290 | 2013-12-18 |
Publications (1)
Publication Number | Publication Date |
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NZ702055A true NZ702055A (en) |
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