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

• US 6,696,570 B2
• Filed: 10/25/2001
• Issued: 02/24/2004
• Est. Priority Date: 11/03/2000
• Status: Expired due to Fees

• Current Assignee: Cytec Technology Corp.
• Original Assignee: Cytec Technology Corp.
• Inventors: Gupta, Ram. B., Sassi, Thomas P.
• Primary Examiner(s): AULAKH, CHARANJIT
• Application Number:
  US10/002,516
• Publication Number:
  US 20020087000A1
• Time in Patent Office: 852 Days
• Field of Search: 546/188, 546/187, 546/186, 546/189, 546/190
• US Class Current: 546/188
• CPC Class Codes: C07D 211/46 having a hydrogen atom as the second substituent in position 4
• CPC Class Codes: C07D 211/58 attached in position 4
• CPC Class Codes: C08K 5/3435 Piperidines

Abstract

Oligomeric compounds and methods of making the compound having the formula:

T—E—F_i—E—F′_j—E′—F_k—E′—F′_l—S  (II)

wherein i, j, k, and l are integers from about 0 to 300 and the sum of i, j, k, and l is greater than 2, wherein the units F, F′ and T are derived from one or more multi-functional carbonyl compounds of general structure

DO—CO—CR^aR^b—(—CR^cR^d—)_n—NH—(Y)_m—CO—OD  (IV)

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; and D is a hydrocarbyl group and the units E, E′ and S are derived from one or more 1-substituted piperidin-4-ol or 4-aminopiperidines of general structure

wherein Z is OH or NHG, wherein G is H or C₁-C₁₂ alkyl, R¹ is —(CH₂)_s-OH, —(CH₂)_s—NH₂, C₁-C₁₈ hydroxyalkoxy or C₅-C₁₂ hydroxycycloalkoxy; wherein s is an integer from 1 to 10; 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. The compounds are useful for stabilizing polymer compositions against photo- and thermal degradation.

Claims

1. A compound having the formula:

2. The compound of claim 1, wherein sum of i, j, k, and l is greater than 6.

3. The compound of claim 1, wherein R₂ is hydrogen, or C₁-C₄ alkyl;

R³, R⁴, R⁵, and R⁶ are a C₁-C₄ alkyl;

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

n is from 4 to 11; and

s is from 2 to 5.

4. The compound of claim 1, wherein R² is hydrogen and R³, R⁴, R⁵, and R⁶ are methyl;

R^a, R^b, R^c, and R^d are each a hydrogen, Z is 0, n is from 4 to 11, m is O, P is O and s is 2.

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

6. The compound of claim 1, wherein the number average molecular weight is from about 400 to 20,000.

7. The compound of claim 1, wherein R² is hydrogen, R³, R⁴, R⁵ and R⁶ are methyl, R^a, R^b, R^c and R^d are each hydrogen, Z is O, n is from 4 to 11 and s is 0.

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

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

9. The method of claim 8, wherein the reaction mixture further comprises a solvent.

10. The method of claim 9, wherein the solvent comprises one or more of benzene, toluene, or one or more xylenes.

11. The method of claim 8, wherein R¹ is —

(CH₂)₂OH;

R³, R⁴, R⁵, and R⁶ are each CH₃; and

R² is H;

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

Z is —

O—

, and n is 4 and D is CH₃.

12. The method of claim 8, wherein the reaction mixture further comprises a catalyst.

13. The method of claim 12, wherein the catalyst comprises a base.

14. The method of claim 12, 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.

15. 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, ^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, 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 an integer from 0 to 20 or CO—

C₆H₄-, and the substitution pattern on the phenylene group may be an ortho, meta, or para substitution pattern, in addition 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 H or C₁-C₁₂ alkyl, R¹ is —

(CH₂)_s-OH, —

(CH₂)_sC₁-C₁₈ hydroxyalkoxy or C₅-C₁₂ hydroxycycloalkoxy, wherein s is an integer from 1 to 10;

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 (II); and

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

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

17. The method of claim 15, wherein the reaction mixture further comprises a catalyst.

18. The method of claim 17, wherein the catalyst comprises a base catalyst.

19. The method of claim 17, wherein the catalyst is 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.

20. The method of claim 15, wherein the reaction is carried out in a solvent.

21. The method of claim 15, wherein the concentration of the one or more lactams is from about 0.075 to 10 M;

the ratio of the one or more lactams to the one or more carbonyl compounds is from about 2;

1 to 1;

4;

the ratio of the one or more lactams to the one or more 1-substituted piperidin-4-ol or 4-aminopiperidines is from about 2;

1 to 1;

2; and

further comprising a catalyst in an amount of less than about 30 mole percent relative to the amount of the one or more carbonyl compounds.

22. The method of claim 15, wherein the lactam comprises caprolactam.

23. The method of claim 15, wherein the lactam comprises laurolactam.