US6696570B2
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US
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Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
Assignee: Cytec Technology Corp
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Filing: 2001-10-25
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Granted: 2004-02-24
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Expires: 2021-10-25
Abstract
Abstract Oligomeric compounds and methods of making the compound having the formula: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 structurewherein 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<e>R<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 structurewherein Z is OH or NHG, wherein G is H or C1-C12 alkyl, R<1 >is -(CH2)s-OH, -(CH2)s-NH2, C1-C18 hydroxyalkoxy or C5-C12 hydroxycycloalkoxy; wherein s is an integer from 1 to 10; R<2 >represents hydrogen, C1-C8 alkyl, or benzyl; R<3>, R<4>, R<5>, and R<6 >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.
Inventors
- 👤 Thomas P. Sassi
- 👤 Ram. B. Gupta
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 20:28
CPC Classifications
C; C07; C07D; C07D211/00; C07D211/04; C07D211/06; C07D211/36; C07D211/40; C07D211/44; C07D211/46; C07D401/00; C07D401/14; C07D211/56; C07D211/58; C08; C08K; C08K5/00; C08K5/16; C08K5/34; C08K5/3412; C08K5/3432; C08K5/3435
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
302 words
A 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 E-F is S is a hydrogen, or a unit derived from a piperidin-4-ol or a 4-aminopiperidine moiety having the structure and T is a hydrogen or a unit derived from a multi-functional carbonyl compound having the structure wherein D is a hydrocarbyl group, n is an integer from 1 to 15, m is either 0 or 1, s is 0 or an integer from 1 to 10; R a , R b , R c , and R d , are each a hydrogen or a hydrocarbyl group; Y is CO—(CR e R 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—C 6 H 4 -, 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; R 2 is hydrogen, C 1 -C 8 alkyl, or benzyl; R 3 , R 4 , R 5 , and R 6 are each a hydrogen, C 1 -C 8 alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached form a C 5 -C 10 cycloalkyl; Z is —O— or NG, wherein G is H or C 1 -C 12 alkyl; and when s is greater than 0, P is NH or O; and when s is 0, P═O or O-L-O, where L is a hydrocarbylene.
Claim 2
Dependent Claim
302 words
A 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 E-F is S is a hydrogen, or a unit derived from a piperidin-4-ol or a 4-aminopiperidine moiety having the structure and T is a hydrogen or a unit derived from a multi-functional carbonyl compound having the structure wherein D is a hydrocarbyl group, n is an integer from 1 to 15, m is either 0 or 1, s is 0 or an integer from 1 to 10; R a , R b , R c , and R d , are each a hydrogen or a hydrocarbyl group; Y is CO—(CR e R 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—C 6 H 4 -, 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; R 2 is hydrogen, C 1 -C 8 alkyl, or benzyl; R 3 , R 4 , R 5 , and R 6 are each a hydrogen, C 1 -C 8 alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached form a C 5 -C 10 cycloalkyl; Z is —O— or NG, wherein G is H or C 1 -C 12 alkyl; and when s is greater than 0, P is NH or O; and when s is 0, P═O or O-L-O, where L is a hydrocarbylene.
Claim 3
Dependent Claim
18 words
The compound of claim 1 , wherein sum of i, j, k, and l is greater than 6.
Claim 4
Dependent Claim
72 words
The compound of claim 1 , wherein R 2 is hydrogen, or C 1 -C 4 alkyl; R 3 , R 4 , R 5 , and R 6 are a C 1 -C 4 alkyl; R a , R b , R c , and R d are each a hydrogen, aromatic, or C 1 -C 4 alkyl; n is from 4 to 11; and s is from 2 to 5.
Claim 5
Dependent Claim
61 words
The compound of claim 1 , wherein R 2 is hydrogen and R 3 , R 4 , R 5 , and R 6 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.
Claim 6
Dependent Claim
7 words
The compound of claim 4 wherein n=4.
Claim 7
Dependent Claim
18 words
The compound of claim 1 , wherein the number average molecular weight is from about 400 to 20,000.
Claim 8
Dependent Claim
51 words
The compound of claim 1 , wherein R 2 is hydrogen, R 3 , R 4 , R 5 and R 6 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.
Claim 9
Dependent Claim
303 words
A method of forming the compound of claim 1 comprising: combining one or more multi-functional carbonyl compounds of general structure DO—CO—CR a R b -(CR c R 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 e R 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—C 6 H 4 -, 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 with one or more 1-substituted piperidin-4-ol or 4-aminopiperidine of general structure wherein Z is OH or NHG, wherein G is H or C 1 -C 12 alkyl, R 1 is —(CH 2 ) s -OH, —(CH 2 ) s —NH 2 , C 1 -C 18 hydroxyalkoxy or C 5 -C 12 hydroxycycloalkoxy, wherein s is an integer from 1 to 10; R 2 represents hydrogen, C 1 -C 8 alkyl, or benzyl; R 3 , R 4 , R 5 , and R 6 are each a hydrogen, C 1 -C 8 alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached form a C 5 -C 10 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.
Claim 10
Dependent Claim
14 words
The method of claim 8 , wherein the reaction mixture further comprises a solvent.
Claim 11
Dependent Claim
21 words
The method of claim 9 , wherein the solvent comprises one or more of benzene, toluene, or one or more xylenes.
Claim 12
Dependent Claim
65 words
The method of claim 8 , wherein R 1 is —(CH 2 ) 2 OH; R 3 , R 4 , R 5 , and R 6 are each CH 3 ; and R 2 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 CH 3 .
Claim 13
Dependent Claim
14 words
The method of claim 8 , wherein the reaction mixture further comprises a catalyst.
Claim 14
Dependent Claim
12 words
The method of claim 12 , wherein the catalyst comprises a base.
Claim 15
Dependent Claim
45 words
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.
Claim 16
Dependent Claim
307 words
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 e R 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—C 6 H 4 -, 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 C 1 -C 12 alkyl, R 1 is —(CH 2 ) s -OH, —(CH 2 ) s C 1 -C 18 hydroxyalkoxy or C 5 -C 12 hydroxycycloalkoxy, wherein s is an integer from 1 to 10; R 2 represents hydrogen, C 1 -C 8 alkyl, or benzyl; R 3 , R 4 , R 5 , and R 6 are each a hydrogen, C 1 -C 8 alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached form a C 5 -C 10 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.
Claim 17
Dependent Claim
33 words
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.
Claim 18
Dependent Claim
14 words
The method of claim 15 , wherein the reaction mixture further comprises a catalyst.
Claim 19
Dependent Claim
13 words
The method of claim 17 , wherein the catalyst comprises a base catalyst.
Claim 20
Dependent Claim
45 words
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.
Claim 21
Dependent Claim
15 words
The method of claim 15 , wherein the reaction is carried out in a solvent.
Claim 22
Dependent Claim
92 words
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.
Claim 23
Dependent Claim
11 words
The method of claim 15 , wherein the lactam comprises caprolactam.
Claim 24
Dependent Claim
11 words
The method of claim 15 , wherein the lactam comprises laurolactam.
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