Hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same

• US 20020099218A1
• Filed: 10/25/2001
• Published: 07/25/2002
• Est. Priority Date: 11/03/2000
• Status: Active Grant

• Current Assignee: Cytec Technology Corp.
• Original Assignee: Cytec Technology Corp.
• Inventors: Gupta, Ram B., Sassi, Thomas P.
• Granted Patent: US 6,492,521 B2
• Time in Patent Office: Days
• US Class Current: 546/233
• CPC Class Codes: C07D 211/46 having a hydrogen atom as the second substituent in position 4
• CPC Class Codes: C08K 5/3435 Piperidines

Abstract

Compounds and methods of preparing compounds of the formula:

RZ—CO—CR^aR^b—(CR^cR^d)_n—NH—(Y)_m—CO—A  (I)

wherein n is an integer from 1 to 15, m is either 0 or 1; R^a, R^b, R^c, and R^d are each a hydrogen or a hydrocarbyl group; Y is CO—(CR^eR^f)_p, wherein R^e and R^f are each a hydrogen or hydrocarbyl group and p is zero or an integer from 1 to 20 or CO—C₆H₄—, wherein the substitution pattern on the phenylene group is an ortho, meta, or para substitution pattern and one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group; Z is —O— or —NG—, wherein G is H, C₁-C₁₂ alkyl or the radical R; wherein R is

wherein R¹ is hydrogen, C₁-C₁₈ alkyl, O, OH, CH₂CN, C₁-C₁₈ alkoxy, C-C₁₈ hydroxyalkoxy, C₅-C₁₂ cycloalkoxy, C₅-C₁₂ hydroxycycloalkoxy, C₃-C₆ alkenyl, C₁-C₁₈ alkynyl, C₇-C₉ phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2 or 3 C₁-C₄ alkyls, or an aliphatic C₁-C₈ acyl; R² is hydrogen, C₁-C₈ alkyl, or benzyl; R³, R⁴, R⁵, and R⁶ are each a hydrogen, C₁-C₈ alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached form a C₅-C₁₀ cycloalkyl; and A is either ZR or a hydrocarbyl group, which are useful for stabilizing polymer compositions against photo- and thermal degradation.

Claims

1. A compound having the formula (I):

RZ—

CO—

CR^aR^b—

(CR^cR^d)—

NH—

(Y)_m—

CO—

A 

 

(I)

wherein n is an integer from 1 to 15, m is either 0 or 1;

R^a, R^b, R^c, and R^d are each a hydrogen or a hydrocarbyl group;

Y is CO—

(CR^eR^f)_p, wherein R^e and R^f are each a hydrogen or hydrocarbyl group and p is zero or an integer from 1 to 20 or CO—

C₆H₄—

, wherein the substitution pattern on the phenylene group is an ortho, meta, or para substitution pattern and one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group;

Z is —

O—

or —

NG—

, wherein G is H, C₁-C₁₂ alkyl or the radical R;

wherein R is

2. The compound of claim 1, wherein R¹ is a H, C₁-C₄ alkyl, O, OH;

C₁-C₁₈ alkoxy, C₁-C₁₈ hydroxyalkoxy, C₅-C₁₂ cycloalkoxy, C₅-C₁₂ hydroxycycloalkoxy;

R² is H, or C₁-C₄ alkyl;

R³, R⁴, R⁵, and R⁶ are each H or C₁-C₄ alkyl;

R^a, R^b, R^c, and R^d, are each a hydrogen, aromatic, or C₁-C₄ alkyl; and

n is from 4 to 11.

3. The compound of claim 1, wherein R¹ is H or CH₃;

R³, R⁴, R⁵, and R⁶ are each CH₃;

R² is hydrogen;

R^a, R^b, R^c and R^d are each a hydrogen;

Z is —

O—

;

m is 0 or 1; and

n is and integer from 4 to 10.

4. The compound of claim 3 wherein A is ZR.

5. The compound of claim 4 wherein n is 4.

6. A method of forming the compound of claim 1 comprising:

combining one or more multi-functional carbonyl compounds of general structure;

DO—

CO—

CR^aR^b—

(CR^cR^d)_n—

NH—

(Y)_m—

CO—

B

wherein n is an integer from 1 to 15, m is either 0 or 1;

R^a, R^b, R^c, and R^d, are each a hydrogen or a hydrocarbyl group;

Y is CO—

(CR^eR^f)_p, wherein R^e and R^f are each a hydrogen or hydrocarbyl group and p is zero or an integer from 1 to 20 or CO—

C₆H₄—

, wherein the substitution pattern on the phenylene group is an ortho, meta, or para substitution pattern and wherein one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group;

D is a hydrocarbyl group; and

B is either OD or D;

with one or more 1-substituted piperidin-4-ol or 4-aminopiperidines of general structure

wherein Z is OH or NHG, wherein G is as defined in claim 1;

R¹ is hydrogen, C₁-C₁₈ alkyl, O, OH, CH₂CN, C₁-C₁₈ alkoxy, C₁-C₁₈ hydroxyalkoxy, C₅-C₁₂ cycloalkoxy, C₅-C₁₂ hydroxycycloalkoxy, C₃-C₆ alkenyl, C₁-C₁₈ alkynyl, C₇-C₉ phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2 or 3 C₁-C₄ alkyls, or an aliphatic C₁-C₈ acyl;

R² represents hydrogen, C₁-C₈ alkyl, or benzyl;

R³, R⁴, R⁵, and R⁶ are each a hydrogen, C₁-C₁₈ alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached form a C₅-C₁₀ cycloalkyl, to form a reaction mixture;

reacting the reaction mixture for a sufficient time to form the compound of formula (I); and

recovering the compound of formula (I) from the reaction mixture.

7. The method of claim 6, wherein the one or more multifunctional carbonyl compounds is present in an amount of about 0.025 to 2.5 M and the molar ratio of the one or more multi-functional carbonyl compounds to the one or more 1-substituted piperidin-4-ol or 4-aminopiperidines is from about 20:

1 to 1;

5.

8. The method of claim 6, wherein the substituted 4-piperidin-4-ol is 1,2,2,6,6-pentamethyl-4-piperidinol or 2,2,6,6-tetramethyl-4-piperidinol and the multi-functional carbonyl compound is selected from the group consisting of methyl 6-(methoxycarbonylamino)hexanoate, butyl 6-(butoxycarbonylamino) undecanoate, methyl 6-(butoxycarbonylamino)undecanoate, butyl 6-(methoxycarbonylamino)undecanoate, methyl 6-(methoxycarbonylamino)undecanoate, and combinations thereof.

9. The method of claim 6, wherein the reaction mixture further comprises a solvent.

10. The method of claim 6, wherein the reaction mixture further comprises a catalyst.

11. The method of claim 10, wherein the catalyst comprises methoxide.

12. The method of claim 10, wherein the catalyst comprises a Lewis acid selected from the group consisting of aluminum trichloride, aluminum tribromide, trimethylaluminum, boron trifluoride, boron trichloride, 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane, zinc dichloride, titanium tetrachloride, titanium (IV) isopropoxide, tin dichloride, tin tetrachloride, a tetraalkoxytitanate, and mixtures thereof.

13. The method of claim 10, wherein the catalyst is present in an amount of less than about 30 mole percent based on the molar quantity of the multi-functional carbonyl compound.

14. A method of forming the compound of claim 1 from a lactam in a single-step comprising:

combining one or more lactams of general structure

wherein n is an integer from 1 to 15 and R^a, R^b, R^c, and R^d are each a hydrogen or a hydrocarbyl group with one or more carbonyl compounds of general structure

wherein m is either 0 or 1, D is a hydrocarbyl group and B is a hydrocarbyl group or OD and Y is CO—

(CR^eR^f)_p, wherein R^e and R^f are each a hydrogen or hydrocarbyl group and p is zero or an integer from 1 to 20 or CO—

C₆H₄—

, and the substitution pattern on the phenylene group may be an ortho, meta, or para substitution pattern, and one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or other functional group; and

one or more 1-substituted piperidin-4-ol or 4-aminopiperidines of general structure

wherein Z is OH or NHG, wherein G is as defined in claim 1;

R¹ is hydrogen, C₁-C₁₈ alkyl, O, OH, CH₂CN, C₁-C₁₈ alkoxy, C₁-C₁₈ hydroxyalkoxy, C₅-C₁₂ cycloalkoxy, C₅-C₁₂ hydroxycycloalkoxy, C₃-C₆ alkenyl, C₁-C₁₈ alkynyl, C₇-C₉ phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2 or 3 C₁-C₄ alkyls, or an aliphatic C₁-C₈ acyl;

R² represents hydrogen, C₁-C₈ alkyl, or benzyl;

R³, R⁴, R⁵, and R⁶ are each a hydrogen, C₁-C₈ alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached, form a C₅-C₁₀ cycloalkyl to provide a reaction mixture;

reacting the reaction mixture for a sufficient time to form the compound of formula (I); and

recovering the compound of formula (I) from the reaction mixture.

15. The method of claim 14 wherein the carbonyl compound is selected from the group consisting of a dialkyl carbonate, a dialkyl oxalate, a dialkyl diester, an alkyl ester, and mixtures thereof.

16. The method of claim 14, wherein the reaction mixture further comprises a catalyst.

17. The method of claim 16, wherein the catalyst comprises a Lewis acid selected from the group consisting of aluminum trichloride, aluminum tribromide, trimethylaluminum, boron trifluoride, boron trichloride, zinc dichloride, titanium tetrachloride, titanium (IV) isopropoxide, tin dichloride, tin tetrachloride, a tetraalkoxytitanate, and mixtures thereof.

18. The method of claim 14, wherein the reaction mixture further comprises a solvent.

19. The method of claim 18, wherein the concentration of lactam is from about 0.025 to 10 M;

the ratio of lactam to carbonyl compound is from about 2;

1 to 1;

4;

the ratio of lactam to 1-substituted piperidin-4-ol or 4-aminopiperidine is from about 1;

1;

to 1;

6; and

further comprising a catalyst in an amount of less than about 30 mole percent relative to the amount of carbonyl compound.

20. The method of claim 16, wherein n is from 3 tol2 and the catalyst comprises a base catalyst or a Lewis acid.

21. The method of claim 14, wherein the lactam comprises caprolactam.

22. The method of claim 14, wherein the lactam comprises laurolactam.

24. The method of claim 23, wherein n is from about 3 to 12.

25. The method of claim 23, wherein the Lewis acid catalyst is selected from the group consisting of aluminum trichloride, aluminum tribromide, trimethylaluminum, boron trifluoride, boron trichloride, zinc dichloride, titanium tetrachloride, titanium (IV) isopropoxide, tin dichloride, tin tetrachloride, a tetraalkoxytitanate, and mixtures thereof.

26. The method of claim 23, wherein the reaction mixture further comprises a solvent.

27. The method of claim 23, wherein the lactam comprises caprolactam.

28. The method of claim 23, wherein the lactam comprises laurolactam.

29. The method of claim 23, wherein the temperature of the reaction mixture when said base catalyst is used is less than 15°

C.

23. A method of forming a multi-functional carbonyl compound having the structure

DO—

CO—

CR^aR^b—

(CR^cR^d)_m—

NH—

(Y)_m—

CO—

B

wherein n is an integer from about 1 to 15, m is either 0 or 1;

R^a, R^b, R^c, and R^d are each a hydrogen or a hydrocarbyl group;

Y is CO—

(CR^eR^f)_p, wherein R^e and R^f are each a hydrogen or hydrocarbyl group and p is an integer from about 0 to 20 or CO—

C₆H₄—

, wherein the substitution pattern on the phenylene group is an ortho, meta, or para substitution pattern and one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group;

D is a hydrocarbyl group; and

B is either OD or D, comprising;

combining one or more lactams of general structure

wherein n and R^a, R^b, R^c, and R^d are as defined above with one or more carbonyl compounds of general structure

wherein D, B, Y, and m are as defined above; and

a Lewis acid catalyst, or a base ca talyst to provide a reaction mixture;

reacting the reaction mixture for a sufficient time to produce the multi-functional carbonyl compound; and

recovering the multi-functional carbonyl compound from the reaction mixture, wherein the temperature of the reaction mixture when said base catalyst is used is less than about 20°

C.