Ultraviolet radiation absorbing polymer composition

Abstract

The present invention includes an ultraviolet radiation absorbing polymer composition comprising the polymer compound of formula ##STR00001##
and compositions containing such an ultraviolet radiation absorbing polymer composition.

Claims

1. Ultraviolet radiation absorbing polymer composition comprising a polymer compound of the formula ##STR00017## wherein the sum of n and m is a number from 3 to 10.

2. The composition according to claim 1, wherein the polymer compound has a weight average molecular weight (M) of about 500 to about 50,000 Da.

3. The composition according to claim 1, wherein the composition additionally comprises at least one component selected from the group consisting of (i) benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-, methyl ester, (ii) benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-, (iii) methanol and (iv) tin.

4. The composition according to claim 3 comprising less than or equal to 1.1 w/w % of benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-, methyl ester.

5. The composition according to claim 3 comprising less than or equal to 1.1 w/w % benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-.

6. The composition according to claim 3 comprising less than or equal to 1.5 w/w % of a combination of benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-, methyl ester.

7. The composition according to claim 3 comprising less than or equal to 700 ppm tin.

8. The composition according to claim 1 essentially free of tin.

9. The composition according to claim 3 comprising less than 3000 ppm methanol.

10. The composition according to claim 1 having a Gardner Value of 1-8.

11. A cosmetic composition comprising the ultraviolet radiation absorbing polymer composition of claim 1.

12. The cosmetic composition according to claim 11, comprising from 0.1 to 50% by weight, based on the total weight of the composition, of the ultraviolet radiation absorbing polymer composition and a cosmetically tolerable adjuvant.

13. The cosmetic composition according to claim 11 or 12 further comprising a UV filter selected from the group consisting of: (1) an aqueous dispersion of 5,6,5,6-tetraphenyl-3,3-(1,4-Phenylene)bis(1,2,4-Triazine) corresponding to the formula ##STR00018## in particulate form; (2) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine; (3) Butyl Methoxydibenzoylmethane; (4) Diethylhexyl Butamido Triazone; (5) Ethylhexyl Triazone; (6) Diethylamino Hydroxy Benzoyl Hexyl Benzoate; (7) Ethylhexyl Methoxycinnamate; (8) Ethylhexyl Salicylate; (9) Homosalate; (10) Octocrylene; (11) Methylene Bis-Benzotriazolyl Tetramethylbutylphenol; (12) Phenylbenzimidazole Sulfonic Acid; (13) Titanium Dioxide; (14) Tris-Biphenyl Triazine; and (15) (2-{4-[2-(4-Diethylamino-2-hydroxy-benzoyl)-benzoyl]-piperazine-1-carbonyl}-phenyl)-(4-diethylamino-2-hydroxy-phenyl)-methanone; (16) BBDAPT; Benzoic acid, 4,4-[[6-[[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]-1 disiloxanyl]propyl]amino]-1,3,5-triazine-2,4-diyl]diimino]bis-, dibutyl ester; (17) benzylidene malonates; (18) merocyanine derivatives; (19) Bis(butylbenzoate) diaminotriazine am inopropylsiloxane; (20) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine) encapsulated in a polymer matrix; (21) 2-(2H-Benzotriazol-2-yl)-6-[(2-ethylhexyloxy)methyl]-4-methylphenol; (22) 2-Propenoic acid, 3-(4-methoxyphenyl)-, 2-methylphenyl ester; and (23) Zinc oxide; wherein said composition also contains a pharmaceutically or cosmetically acceptable excipient.

Description

EXAMPLES

(1) Polyglycerol

(2) Polyglycerol is prepared as described in WO 2002 036534, US 2002 0058781 and U.S. Pat. No. 6,620,904. CaO or Ca(OH).sub.2 is used as catalyst. Glycerol, diglycerol and other low molecular fractions are removed from the reaction product e.g. by short path distillation in order to achieve a specific quality.

(3) Properties of polyglycerol: yellow to brown material; very high viscosity at room temperature, hydroxyl-value 800-1000, water content<0.2%, glycerol and diglycerols<5.5% (determined by GC after derivatization with a silylating agent).

Example A1: Transesterification Product of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid with Polyglycerol

(4) 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid (605.8 g) is charged into a glass reactor equipped with nitrogen inlet, dephlegmator (120 C.) and agitation. The temperature is set to 227 C. in order to melt the 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid. As soon as the 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid is completely melted, tin-(II)-2-ethylhexanoate (0.48 g) is added and the reactor is evacuated to 860 mbar. Molten polyglycerol (207.1 g) is charged within 1 h, while maintaining a reaction temperature of 220-225 C. and a pressure of 30 mbar. Methanol is distilled of. Thereafter the vacuum is reduced gradually to 5-8 mbar at 225 C. and the reaction mass is stirred for 16-18 h, until the total concentration of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid is below 1.0%. The composition of the reaction mixture is monitored by HPLC. After cooling down to ambient temperature, the UV-absorbing polymer composition (756.3 g) is obtained as a yellow to amber glassy solid.

(5) TABLE-US-00005 HPLC (unbound chromophore) Compound % 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- propanoic acid methyl ester 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- propanoic acid Sum <1%
a

(6) TABLE-US-00006 Solubility Solvent % C12-15 alkyl benzoate >40 Dibutyl adipate >40 Dicaprylyl carbonate >40

Example A2: Ultraviolet Radiation Absorbing Composition: Transesterification Product of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid methyl ester with polyglycerol

(7) 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester (630.9 g) is charged into a glass reactor equipped with nitrogen inlet, dephlegmator (120 C.) and agitation. The temperature is set to 227 C. in order to melt the 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester. As soon as the 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester is completely melted, tin-(II)-2-ethylhexanoate (0.48 g) is added and the reactor is evacuated to 860 mbar. Molten polyglycerol (206.9 g) is charged within 1 h, while maintaining a reaction temperature of 220-225 C. and a pressure of 30 mbar. Methanol is distilled of. Thereafter the vacuum is reduced gradually to 5-8 mbar at 225 C. and the reaction mass is stirred for 16-18 h, until the total concentration of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid is below 1.0%. The composition of the reaction mixture is monitored by HPLC. After cooling down to ambient temperature, the UV-absorbing polymer composition (750.3 g) is obtained as a yellow to amber glassy solid.

(8) TABLE-US-00007 HPLC (unbound chromophore) Compound % 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- 0.2 propanoic acid methyl ester 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- 0.6 propanoicVacid Sum 0.8 UV E Wavelength (1%, Solubility (nm) 1 cm) Solvent % GPC 344 336 C12-15 alkyl >40 Peak RV - (ml) 18.4 benzoate Dibutyl adipate >40 Mn - (Daltons) 872 Dicaprylyl >40 Mw - (Daltons) 1577 carbonate Mz - (Daltons) 2370 Mp - (Daltons) 1341 Mw/Mn 1.80

Example A3: Ultraviolet Radiation Absorbing Composition: Transesterification Product of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid methyl ester with polyglycerol

(9) 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester (630.84 g, 1.785 mol) is charged into a glass reactor equipped with nitrogen inlet, dephlegmator (120 C.) and agitation. The temperature is set to 197 C. in order to melt the 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester. As soon as the 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester is completely melted, tin-(II)-2-ethylhexanoate (0.47 g, 1.2 mmol) is added and the reactor is evacuated to 850 mbar. Molten polyglycerol (206.3 g) is charged within 1 h, while maintaining a reaction temperature of 185-190 C. Methanol is distilled of. Thereafter the vacuum is reduced gradually to 5-8 mbar at 197 C. and the reaction mass is stirred for 48 h, until the total concentration of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid is below 1.0%. The composition of the reaction mixture is monitored by HPLC. After cooling down to ambient temperature, the UV-absorbing polymer composition (748.5 g) is obtained as a yellow to amber glassy solid.

(10) TABLE-US-00008 HPLC (unbound chromophore) Compound % 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- 0.1 propanoic acid methyl ester 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- 0.5 propanoic acid Sum 0.6 UV Wavelength E (1%, Solubility GPC (nm) 1 cm) Solvent % Peak RV - (ml) 18.16 300 346 C12-15 alkyl >40 Mn - (Daltons) 911 benzoate 320 284 Dibutyl adipate >40 Mw - (Daltons) 1584 340 342 Dicaprylyl >40 Mz - (Daltons) 2277 carbonate 360 263 Mp - (Daltons) 1383 380 70 Mw/Mn 1.74 400 1 344 345 343 345 303 351

Example A4: Ultraviolet Radiation Absorbing Composition: Transesterification Product of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid methyl ester with polyglycerol

(11) A 100 ml glass flask is placed in an agitating heating block and polyglycerol (2.9 g) is transferred into the flask. 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester (8.8 g, 25 mmol) and tin-(II)-2-ethylhexanoate (0.029 g, 0.072 mmol) is added. The mixture is melted and heated up to 195 C. under a nitrogen flow. Thereafter the apparatus is slowly evacuated to a pressure of 5 mbar. The reaction mixture is stirred vigorously under vacuum at 195 C. for approx. 16 h and at 250 C. for approx. 24 h. After cooling down to ambient temperature, the UV-absorbing polymer composition (10.3 g) is obtained as a brown glassy solid.

(12) TABLE-US-00009 HPLC (unbound chromophore) Compound % 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- 0 propanoic acid methyl ester 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- 1.0 propanoic acid Sum 1.0 Solubility GPC Solvent % Peak RV - (ml) 18.1 C12-15 alkyl benzoate >40 Mn - (Daltons) 1679 Dibutyl adipate >40 Mw - (Daltons) 3160 Dicaprylyl carbonate >40 Mz - (Daltons) 5669 Mp - (Daltons) 1738 Mw/Mn 1.88

Example A5: Ultraviolet Radiation Absorbing Composition: Transesterification Product of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid methyl ester with polyglycerol

(13) 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester (1000.0 g) is charged into a glass reactor equipped with nitrogen inlet, dephlegmator (120 C.) and agitation. The temperature is set to 191 C. in order to melt the 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester. As soon as the 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester is completely melted, the reactor is evacuated to 850 mbar. Molten polyglycerol (325.7 g) is charged within 1 h, while maintaining a reaction temperature of 185-190 C. Methanol is distilled of. Thereafter the vacuum is reduced gradually to 5-8 mbar at 197 C. and the reaction mass is stirred for 44 h, until the total concentration of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid is below 1.0%. The composition of the reaction mixture is monitored by HPLC. After cooling down to ambient temperature, the UV-absorbing polymer composition (1200 g) is obtained as a yellow to amber glassy solid.

(14) TABLE-US-00010 HPLC (unbound chromophore) Compound % 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- 0.25 propanoic acid methyl ester 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- 0.5 propanoic acid Sum 0.75 UV Wavelength E (1%, Solubility (nm) 1 cm) Solvent % GPC 300 354 C12-15 alkyl >40 Peak RV - (ml) 18.3 benzoate 320 292 Dibutyl adipate >40 Mn - (Daltons) 899 340 351 Dicaprylyl >40 Mw - (Daltons) 1573 carbonate 360 269 Mz - (Daltons) 2300 380 73 Mp - (Daltons) 1354 400 4 Mw/Mn 1.75 344 354 344 354 303 359

Example A6: Ultraviolet Radiation Absorbing Composition: Transesterification Product of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid methyl ester with polyglycerol

(15) 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester (306.0 kg) is charged into a glass-lined steel reactor equipped with argon inlet, dephlegmator (120 C.) and agitation. The temperature is set to 195 C. in order to melt the 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester. As soon as the 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester is completely melted, the reactor is evacuated to 850 mbar and tin-(II)-2-ethylhexanoate (20.0 kg) is added. Molten polyglycerol (105.0 kg) is charged within 1-2 h, while maintaining a reaction temperature of 185-190 C. Methanol is distilled of. Thereafter the vacuum is reduced gradually to 5-8 mbar at 195 C. and the reaction mass is stirred for 72 h until the total concentration of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid is below 1.0%. The composition of the reaction mixture is monitored by HPLC. After cooling down to ambient temperature, the UV-absorbing polymer composition (384 kg) is obtained as a yellow to amber glassy solid.

(16) TABLE-US-00011 Compound % HPLC analysis of the reaction product (unbound chromophore) 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- 0.1 propanoic acid methyl ester 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- 0.5 propanoic acid Sum 0.6 HPLC analysis of the completely hydrolyzed reaction product 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- 75.8 propanoic acid
Amount of covalently Bound Chromophore

(17) 75.8%0.6%=75.2% (chromophore, determined as 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid).

(18) TABLE-US-00012 UV Solubility in E 1%, 1 cm cosmetic solvents ( = 344 nm) 331 Solvent % GPC Methanol 6 C12-15 alkyl >40 Peak RV - (ml) 18.2 (ppm) benzoate T.sub.g ( C.) 51.2 Dibutyl adipate >40 Mn - (Daltons) 756 Sn (ppm) 150 Dicaprylyl >40 Mw - (Daltons) 1464 carbonate Gardner color 6.2 Mz - (Daltons) 2153 scale Mp - (Daltons) 1320 Mw/Mn 1.94