Ultraviolet radiation absorbing polymer composition

Abstract

Disclosed is a method for preparing an ultraviolet radiation absorbing polymer composition comprising the polymer compound of formula ##STR00001##
in an esterification/transesterification which method comprises the steps of reacting a polyglycerol intermediate of formula ##STR00002##
with a benzotriazole UV-chromophore comprising a complementary functional group of formula ##STR00003##
to form the polymer compound of formula (3).

Claims

1. A method for preparing an ultraviolet radiation absorbing polymer composition comprising a polymer compound of formula (3) in an esterification/trans-esterification, which method comprises the steps of reacting a polyglycerol intermediate (2) with a benzotriazole UV-chromophore (1) comprising a complementary functional group to form the UV absorbing polyether compound (3) according to the following reaction scheme: ##STR00017## wherein A is hydrogen; or C.sub.1-C.sub.8alkyl; and k is a number from 2 to 20; and n and m, independently from each other are a number from 0 to 20; wherein at least one of m and n is ≥1.

2. The method according to claim 1, wherein the weight average molecular weight of the polyether of formula (3) is >500.

3. The method according to claim 1, further comprising removing water or alcohol formed during the reaction by distillation during the esterification/transesterification reaction.

4. The method according to claim 1, wherein the esterification/transesterification is carried out at a temperature of 160-270° C.

5. The method according to claim 1, wherein the esterification/transesterification is carried out without any additional solvent.

6. The method according to claim 1, wherein the esterification/transesterification is carried out without additional esterification/transesterification catalysts.

7. The method according to claim 1, wherein the esterification/transesterification is carried out under intermittent or constant vacuum of less than 250 mbar.

8. The method according to claim 1, wherein the esterification/transesterification is carried out at a temperature of 190-260 ° C. for at least 16h.

9. The method according to claim 1, wherein the polyglycerol contains less than 5% of glycerol or linear and cyclic diglycerols.

10. The method according to claim 1, wherein the hydroxyl value of polyglycerol is in the range between 700 and 1100.

11. The method according to claim 1, wherein the benzotriazole UV-chromophore is benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy—.

12. The method according to claim 1, wherein the benzotriazole UV-chromophore is benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy—,methyl ester.

13. The method according to claim 1, wherein the final reaction product is used without further purification.

14. The method according to claim 12, wherein 1 part of polyglycerol is reacted with 2.8-3.2 parts of Benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy—, methyl ester.

15. The method according to claim 11, wherein 1 part of polyglycerol is reacted with 2.8-3.2 parts of Benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy—.

16. The method according to claim 1, wherein the weight average molecular weight of the polyether of formula (3) is from 1,000 to 20,000.

17. The method according to claim 1, wherein the weight average molecular weight of the polyether of formula (3) is from 1,000 to 10,000.

18. The method according to claim 1, wherein the esterification/transesterification is carried out at a temperature of 190-260° C.

19. The method according to claim 1, wherein the esterification/transesterification is carried out under intermittent or constant vacuum of less than 100 mbar.

20. The method according to claim 1, wherein the hydroxyl value of polyglycerol is in the range between 750 and 900.

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-ethyl-hexanoate (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-00006 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-00007 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%.

(8) 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.

(9) TABLE-US-00008 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 propanoic acid Sum 0.8

(10) TABLE-US-00009 UV Wave- E length (1%, Solubility GPC (nm) 1 cm) Solvent % Peak RV - (ml) 18.4 344 336 C12-15 alkyl benzoate >40 Dibutyl adipate >40 Mn - (Daltons) 872 Dicaprylyl carbonate >40 Mw - (Daltons) 1577 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

(11) 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.

(12) TABLE-US-00010 HPLC (unbound chromophore) Compound % 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 0.1 benzene-propanoic acid methyl ester 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 0.5 benzene-propanoic acid Sum 0.6

(13) TABLE-US-00011 UV Wave- E length (1%, Solubility GPC (nm) 1 cm) Solvent % Peak RV - (ml) 18.16 300 346 C12-15 alkyl benzoate >40 Mn - (Daltons) 911 320 284 Dibutyl adipate >40 Mw - (Daltons) 1584 340 342 Dicaprylyl carbonate >40 Mz - (Daltons) 2277 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

(14) 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.

(15) TABLE-US-00012 HPLC (unbound chromophore) Compound % 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 0 benzene-propanoic acid methyl ester 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 1.0 benzene-propanoic acid Sum 1.0

(16) TABLE-US-00013 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

(17) 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.

(18) TABLE-US-00014 HPLC (unbound chromophore) Compound % 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 0.25 benzene-propanoic acid methyl ester 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 0.5 benzene-propanoic acid Sum 0.75

(19) TABLE-US-00015 UV Wavelength E Solubility (nm) (1%, 1 cm) Solvent % GPC 300 354 C12-15 alkyl benzoate >40 Peak RV-(ml) 18.3 320 292 Dibutyl adipate >40 Mn-(Daltons) 899 340 351 Dicaprylyl carbonate >40 Mw-(Daltons) 1573 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

(20) 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.

(21) TABLE-US-00016 HPLC analysis of the reaction product (unbound chromophore) Compound % 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 0.1 benzene-propanoic acid methyl ester 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 0.5 benzene-propanoic acid Sum 0.6

(22) TABLE-US-00017 HPLC analysis of the completely hydrolized reaction product Compound % 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 75.8 benzene-propanoic acid

(23) Amount of Covalentely Bound Chromophore

(24) 75.8%−0.6%=75.2% (chromophore, determined as 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid).

(25) TABLE-US-00018 UV Solubility in E 1%, 1 cm cosmetic solvents GPC (λ = 344 nm) 331 Solvent % Peak RV - (ml) 18.2 Methanol 6 C12-15 alkyl >40 (ppm) benzoate T.sub.g (° C.) 51.2 Dibutyl adipate >40 Mn - (Daltons) 756 Sn (ppm) 150 Dicaprylyl >40 Mw - (Daltons) 1464 carbonate Gardner 6.2 Mz - (Daltons) 2153 color scale Mp - (Daltons) 1320 Mw/Mn 1.94