Hydroxy-substituted N-alkoxy hindered amines and compositions

44 Pages·2013·4.04 MB·English

US006271377B1
(12) United States Patent (10) Patent N0.: US 6,271,377 B1
Galbo et al. (45) Date of Patent: Aug. 7, 2001
(54) HYDROXY-SUBSTITUTED N-ALKOXY (56) References Cited
HINDERED AMINES AND COMPOSITIONS
STABILIZED THEREWITH U'S' PATENT DOCUMENTS
4,972,009 11/1990 Suhadolnik et a1. ................. .. 524/99
(75) Inventors: James P. Galbo, Wingdale, NY (US); 5,004,770 4/1991 Cortolano et a1. .. 524/99
(GUesr)a.l dN aAnIc cya pNo_c cClii,f fG rReiennwgiwcoho,d NJ 55,,200946,,497530 43//11999932 WGianltbeor 6e1t8 .1a.l . . 546/188
(Us)? Robert E_ Detl’efsen pumgm 5,627,248 5/1997 Koster et a1. ...................... .. 526/217
Valley, NY (US); Michael P. DiFazio, FOREIGN PATENT DOCUMENTS
Mobile, AL (US); Ramanathan
Ravichandran, Nanuet; Peter Solera, '
Suffern, both of NY (US) '
OTHER PUBLICATIONS
(73) Assignee: Ciba Specialty Chemicals Hawker et al., J. Am. Chem. Soc. 1996, 118, pp.
Corporation, TarrytoWn, NY
N~ tllch .S .T .F d S .1197672
( * ) Notice: Subject to any disclaimer, the term of this pg'ggglzijzgéw' em 0C ’ fans ara ay 0C ’ ’ ’ ’
patent is extended or adjusted under 35 AS t 1 I t J R d- t B 1 1976 29 211_219
U‘SC. 154(k)) byo days‘ mas e a ., n. . a 1a. 10 ., , , pp. .
Primary Examiner—Richard L. Raymond
(21) Ap p1 N O _ 09/257 711 (74) Attorney, Agent, or Firm—Luther A. R. Hall
. .. ,
(22) Filed: Feb. 25, 1999 (57) ABSTRACT
Hindered amines substituted on the N-atom With an
(51) Int. Cl.7 ........................... .. C07D 211/74; C07F 7/18
—O—E—OH moiety are particularly effective in stabilizing
(52) US. Cl. ............................ .. 546/14; 546/19; 546/186; polyole?n and automotive coating compositions against the
546/188; 546/189; 546/190; 546/191; 546/198;
deleterious effects of oXidative, thermal and actinic radiation
546/208; 546/209; 546/212; 546/228; 546/244;
Where the presence of the OH group on the compounds adds
546/245
important properties not attainable by the use of normal
(58) Field of Search .............................. .. 546/14, 19, 186, —O—E moieties.
546/188, 189, 190, 191, 198, 208, 209,
212, 228, 242, 244, 245 8 Claims, N0 Drawings
US 6,271,377 B1
1 2
HYDROXY-SUBSTITUTED N-ALKOXY because of interaction With the polymer substrate or acid
HINDERED AMINES AND COMPOSITIONS catalytic system needed for curing such substrate.
STABILIZED THEREWITH Examples of polyole?n compositions in Which the instant
compounds are effective include ?ame retardant polyole?ns
The instant invention pertains to hindered amine com Where acidic residues from the decomposition of the halo
pounds Which are substituted on the N-atom by N-alkoxy genated ?ame retardants deactivate hindered amines not
moieties containing one to three hydroxyl groups. These having the N—OR group, greenhouse ?lms and agricultural
materials are particularly effective in stabilizing polyole?ns, mulch ?lms Where acidic residues from pesticides interfere
especially thermoplastic polyole?ns, against the deleterious
With the activity of “normal” hindered amine stabiliZers, and
effects of oxidative, thermal and actinic radiation. The 10 in thermoplastic polyole?ns Where pigment interactions
compounds are also effective in stabilizing acid catalyZed With basic hindered amine stabiliZers interfere With painting
and ambient cured coatings systems. the substrate surfaces. Examples of coating compositions in
Which the instant compounds are effective include melamine
BACKGROUND OF THE INVENTION
crosslinked thermoset acrylic resins, Which are cured using
4-Hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 15 strong acids that interact With basic hindered amine stabi
4-oxo-1-oxyl-2,2,6,6-tetramethylpiperidine are reported to liZers. The instant compounds are also effective in acrylic
alkyd or polyester resins With isocyanate crosslinking
have been used to trap carbon centered radicals formed from
methanol, ethanol, isopropanol and sec-butanol by S. Nigam agents, and in epoxy resins With carboxylic acid, anhydride,
et al., J. Chem. Soc., Trans. Faraday Soc. 1, 1976, 72, 2324 or amine crosslinking agents.
20
and by K.-D. Asmus et al., Int. J. Radiat. Biol., 1976, 29, While the unsubstituted N—OR compounds described in
211. US. Pat. Nos. 5,004,770 and 5,096,950 also perform Well in
US. Pat. No. 5,627,248 and European Patent Application the compositions described in the paragraph above, the
No. 135,280 A2 describe, respectively, difunctional and instant compounds differ signi?cantly in both structure and
monofunctional living free radical polymeriZation initiators, in performance from the prior art compounds by virtue of the
25
some of Which contain hindered amine ethers substituted by presence of the one to three free hydroxy groups present on
hydroxy groups. These compounds differ substantially in the N-alkoxy moiety. These hydroxyl groups in the instant
structure and performance from the instant compounds. compounds provide said compounds With superior antistatic
European Patent Application No. 427,672 A1 and US. properties, compatibility in more polar environments such as
polyurethane based and in Water-borne automotive coating
Pat. No. 4,972,009 mention, but do not exemplify, 30
systems, and in stabiliZing painted automotive thermoplastic
respectively, hydroxylamine and nitrone structures, some of
Which contain C1—C4 hydroxyalkoxy substituted 2,2,6,6 ole?n structures.
tetramethylpiperidine derivatives. Such structures are out The instant compounds are particularly suited for
side the scope of the instant invention. (a) providing superior compatibility in polycarbonates
US. Pat. No. 5,204,473 describes N-hydrocarbyloxy hin 35 and polycarbonate/ABS blends compared to the
dered amine derivatives that are prepared exclusively from N—OE prior art compounds; and
organic compounds containing only carbon and hydrogen
(b) providing superior compatibility in polyesters and
atoms. Such compounds are structurally quite different from
polyamides compared to the prior art N—OE com
the instant compounds. pounds.
US. Pat. No. 5,004,770 describes hindered amine com 40
pounds Which are substituted on the N-atom by alkoxy
OBJECTS OF THE INVENTION
moieties Which alkoxy groups are themselves unsubstituted.
These compounds are especially useful in polymers includ There are tWo objects to the instant invention Which are:
ing polybutadiene, polystyrene, ABS, polyacetal,
1. Novel compounds having on the 1-position of the
polyamide, polyester, polyurethane and polycaronate. 45
hindered amine a moiety —O—E—OH Where the OH
US. Pat. No. 5,096,950 also describes hindered amine group provides important properties; and
compounds Which are substituted on the N-atom by alkoxy
2. Compositions stabiliZed by the novel compounds
moieties Which alkoxy groups are themselves unsubstituted.
described above.
These compounds are found to be useful in polyole?ns.
50
The instant compounds are N-alkoxy substituted deriva
DETAILED DISCLOSURE
tives of 2,2,6,6-tetraalkylpiperidines Where the alkoxy group
is substituted by one to three hydroxy moieties. The instant The instant invention pertains to novel compounds having
compounds also comprise N-alkoxy bridged derivatives of 1-alkoxy substituted hindered amine derivatives Where the
the 2,2,6,6-tetraalkylpiperidines Where the alkoxy moiety, 55 alkoxy moiety is substituted by one to three hydroxy groups
Which is substituted by one to three hydroxy groups, is as described in formulas (1) to (15); or to novel compounds
shared by tWo hindered amine molecules. The free hydroxy having 1-alkoxy bridged hindered amine derivatives Where
moieties of these compounds may be reacted With carboxy the alkoxy moiety, substituted by one to three hydroxy
lic acids, acid chlorides or esters to form simple esters or groups, is shared by tWo hindered amine molecules as
polyesters, or With isocyanates to form urethanes or poly 60 described in formulas (16) to (28); or to oligomeric or
urethanes. polymeric hindered amine molecules made from the reaction
The instant compounds, because of their loW bascity of dialkyl esters or isocyanates With hydroxy substituted
Which is shared by the simple unsubstituted N-alkoxy com N-alkoxy derivatives of 4-hydroxy-2,2,6,6
pounds cited in the tWo patents mentioned above, are of tetraalkylpiperidine as described in formula (29); or to
particular value in the stabiliZation of polyole?ns and auto 65 simple diester or urethane derivatives of hydroxy substituted
motive coating compositions Where the activity of the more N-alkoxy derivatives of 4-hydroxy-2,2,6,6
basic hindered amine stabiliZes is signi?cantly reduced tetramethylpiperidine as described in formula (30)

US 6,271,377 B1
9 10
-continued
(26)
_ R7 G1 G2
>—N
N/ \>—R9 N—O L—(OH)b
—N
R3 G1 G2
— 2
(27)
_ R? /R10
G1 G2 N—(CH2)q—N G1 G2
N2 *1,
(HO)b—E—O—N R9‘</ \N N/ \>iR9 N—O L—(OH)b
N:< >:N
G1 G2 R7 R7 G1 G2
_ 2
(28) (29)
_ R13 G1 G2
. O O
R14_(CH2)11—(O)‘1—51—(O)‘1—(CH2)11—R14 T4 0
((|:H2)k H N—O—G—O R27 0R28
H R9
G1 G2
G1 G1
G; N G;
_ L—(OH)b
(30)
G1 G2
‘IT
R29—C—O N—O—G—O—C—R29
G1 G2
G1 and G2 are independently alkyl of 1 to 4 carbon atoms, 18 carbon atoms, glycidyl, 2,3-dihydroXypropyl,
or G1 and G2 together are pentamethylene; preferably 45 2-hydroxy or Z-(hydroxymethyl) substituted alkyl of 3
G1 and G2 are each methyl; to 12 carbon atoms Which alkyl is interrupted by
E is a straight or branched chain alkylene of 1 to 18 carbon oxygen, an acyl radical of an aliphatic or unsaturated
atoms, cycloalkylene of 5 to 18 Carbon @toms, cycloalk- aliphatic carboXylic or carbamic acid containing 2 to 18
enylene of 5 to 18 Carbon atoms, a Stralght or branched carbon atoms, an acyl radical of a cycloaliphatic car
Chaln alkylene of 1 to 4 Carbon atoms Substltuted by 50 boXylic or carbamic acid containing 7 to 12 carbon
phenyl or by phenyl substituted by one or tWo alkyl
atoms, or acyl radical of an aromatic acid containing 7
groups of 1 to 4 carbon atoms; to 15 carbon atoms;
b is 1, 2 or 3 With the proviso that b cannot exceed the
When n is 2,
number of carbon atoms in E or L, and When b is 2 or _ _
3, each hydroXyl group is attached to a different carbon 55 R3 15 alkylene of 2 to 18 Carbon atoms> a dlvalent acyl
atom of E or L; the two hindered amine groups are radical of an aliphatic or unsaturated aliphatic dicar
generally, but not always, attached to two different boXylic or dicarbamic acid containing 2 to 18 carbon
carbon atoms of L; atoms, a divalent acyl radical of a cycloaliphatic dicar
in each of the formulas (1) to (15) boXylic or dicarbamic acid containing 7 to 12 carbon
m is 0 or 1; 60 atoms, or a divalent acyl radical of an aromatic dicar
R1 is hydrogen, hydroxyl or hydroxymethyh boXylic acid containing 8 to 15 carbon atoms;
R2 is hydrogen, alkyl of 1 to 12 carbon atoms or alkenyl When I1 iS 3,
of 2 to 12 carbon atoms; R3 is a trivalent acyl radical of an aliphatic or unsaturated
n is 1 to 4; aliphatic tricarboXylic acid containing 6 to 18 carbon
When n is 1, 65 atoms, or a trivalent acyl radical of an aromatic tricar
R3 is alkyl of 1 to 18 carbon atoms, alkoxycarbonylalky- boxylic acid Containing 9 to 15 carbon atoms;
lenecarbonyl of 4 to 18 carbon atoms, alkenyl of 2 to When n is 4,
US 6,271,377 B1
11 12
R3 is a tetravalent acyl radical of an aliphatic or unsat
urated aliphatic tetracarboXylic acid, especially 1,2,3,
4-butanetetracarboXylic acid, 1,2,3,4-but-2
enetetracarboXylic acid, 1,2,3,5-pentanetetracarboXylic
acid and 1,2,4,5-pentanetetracarboXylic acid, or R3 is a
tetravalent acyl radical of an aromatic tetracarboXylic
acid containing 10 to 18 carbon atoms;
pis1to3,
R4 is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 10 R10 is hydrogen or methyl,
2 to 6 carbon atoms;
q is 2 to 8,
When p is 1,
RM and R12 are independently hydrogen or the group T2
R5 is hydrogen, alkyl of 1 to 18 carbon atoms, an acyl
radical of an aliphatic or unsaturated aliphatic carboXy 15
lic or carbarnic acid containing 2 to 18 carbon atoms,
an acyl radical of a cycloaliphatic carboXylic or car
barnic acid containing 7 to 12 carbon atoms, an acyl
radical of an aromatic carboXylic acid containing 7 to
20
15 carbon atoms, or R4 and R5 together are —(CH2)
5CO—, phthaloyl or a divalent acyl radical of rnaleic
acid;
When p is 2,
25
R5 is alkylene of 2 to 12 carbon atoms, a divalent acyl
radical of an aliphatic or unsaturated aliphatic dicar
boXylic or dicarbarnic add containing 2 to 18 carbon
atoms, a divalent acyl radical of a cycloaliphatic dicar
boXylic or dicarbarnic acid containing 7 to 12 carbon 30 R13 is hydrogen, phenyl, straight or branched alkyl of 1 to
atoms, or a divalent acyl radical of an aromatic dicar 12 carbon atoms, alkoXy of 1 to 12 carbon atoms,
boXylic acid containing 8 to 15 carbon atoms; straight or branched alkyl of 1 to 4 carbon atoms
When p is 3, substituted by phenyl, cycloalkyl of 5 to 8 carbon
atoms, cycloalkenyl of 5 to 8 carbon atoms, alkenyl of
R5 is a trivalent acyl radical of an aliphatic or unsaturated 35
2 to 12 carbon atoms, glycidyl, allyloXy, straight or
aliphatic tricarboXylic acid containing 6 to 18 carbon
branched hydroXyalkyl of 1 to 4 carbon atoms, or silyl
atoms, or a trivalent acyl radical of an aromatic tricar
or silyloXy substituted three times independently by
boXylic acid containing 9 to 15 carbon atoms;
hydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms
When n is 1, or by alkoXy of 1 to 4 carbon atoms;
40
R6 is alkoXy of 1 to 18 carbon atoms, alkenyloXy of 2 to R14 is hydrogen or silyl substituted three times indepen
18 carbon atoms, —NHalkyl of 1 to 18 carbon atoms dently by hydrogen, by phenyl, by alkyl of 1 to 4
or —N(alkyl)2 of 2 to 36 carbon atoms, carbon atoms or by alkoXy of 1 to 4 carbon atoms;
When n is 2, d is 0 or 1;
45
R6 is alkylenedioXy of 2 to 18 carbon atoms, alkenylene h is 0 to 4;
dioXy of 2 to 18 carbon atoms, —NH-alkylene-NH— k is 0 to 5;
of 2 to 18 carbon atoms or —N(alkyl)-alkylene-N X is 3 to 6;
(alkyl)- of 2 to 18 carbon atoms, or R6 is 4-rnethyl-1,
y is 1 to 10;
3-phenylenediarnino, 50
Z is an integer such that the compound has a molecular
When n is 3, Weight of 1000 to 4000 arnu,
R6 is a trivalent alkoXy radical of a saturated or unsatur R15 is rnorpholino, piperidino, 1-piperiZinyl, alkylarnino
ated aliphatic triol containing 3 to 18 carbon atoms, of 1 to 8 carbon atoms, especially branched alkylarnino
When n is 4, 55 of 3 to 8 carbon atoms such as tert-octylarnino,
—N(alkyl)T1 With alkyl of 1 to 8 carbon atoms, or
R6 is a tetravalent alkoXy radical of a saturated or unsat
—N(all<yl)2 of 2 to 16 carbon atoms,
urated aliphatic tetraol containing 4 to 18 carbon atoms,
R16 is hydrogen, acyl of 2 to 4 carbon atoms, carbarnoyl
R7 and R8 are independently chlorine, alkoXy of 1 to 18 substituted by alkyl of 1 to 4 carbon atoms, s-triaZinyl
carbon atoms, —O—T1, arnino substituted by 60 substituted once by chlorine and once by R15, or
2-hydroXyethyl, —NH(alkyl) of 1 to 18 carbon atoms, s-triaZinyl substituted tWice by R15 With the condition
—N(alkyl)T1 With alkyl of 1 to 18 carbon atoms, or that the tWo R15 substituents may be different;
—N(all<yl)2 of 2 to 36 carbon atoms, R17 is chlorine, arnino substituted by alkyl of 1 to 8 carbon
R9 is a divalent oxygen atom, or R9 is a divalent nitrogen 65 atoms or by T1, —N(alkyl)T1 With alkyl of 1 to 8
atom substituted by either hydrogen, alkyl of 1 to 12 carbon atoms, —N(all<yl)2 of 2 to 16 carbon atoms, or
carbon atoms or T1 the group T3
US 6,271,377 B1
14
R26 is alkylenedioXy of 2 to 18 carbon atoms, alkenylene
dioXy of 2 to 18 carbon atoms, —NH-alkylene-NH—
of 2 to 18 carbon atoms or —N(alkyl)-alkylene-N
(alkyl)- of 3 to 18 carbon atoms,
in formulas (29) and (30), G is a carbon centered diradical
derived from a primary, secondary or tertiary alcohol
G—OH, Where
Z is as de?ned above, and
G is straight or branched chain alkylene of 1 to 18 carbon
10 atoms, cycloalkylene of 5 to 8 carbon atoms, cycloalk
enylene of 5 to 8 carbon atoms, alkenylene of 3 to 18
R18 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl carbon atoms, a straight or branched chain alkylene of
substituted by alkyl of 1 to 4 carbon atoms, s-triaZinyl 1 to 4 carbon atoms substituted by phenyl or by phenyl
substituted tWice by —N(alkyl)2 of 2 to 16 carbon
substituted by one or tWo alkyl of 1 to 4 carbon atoms,
atoms or s-triaZinyl substituted tWice by —N(alkyl)T1 15 With the proviso that in formula (29) successive hin
With alkyl of 1 to 8 carbon atoms; dered amine moieties can be oriented in either a head
L is straight or branched chain alkylene of 1 to 18 carbon to head or head to tail fashion;
atoms, cycloalkylene of 5 to 8 carbon atoms, cycloalk T4 is hydrogen or
enylene of 5 to 8 carbon atoms, alkenylene of 3 to 18
carbon atoms, a straight or branched chain alkylene of
1 to 4 carbon atoms substituted by phenyl or by phenyl
substituted by one or tWo alkyl of 1 to 4 carbon atoms,
in formulas (16) to (28), R1, R2, R7, R8, R9, R10, R13, R14,
d, h, k, m, q, and T1 have the same meanings as in
25 R27 is a straight or branched chain alkylene of 1 to 18
formulas (1) to (15);
carbon atoms, cycloalkylene or cycdoalkenylene of 5 to
R19 is hydrogen, alkyl of 1 to 18 carbon atoms, alkenyl of 8 carbon atoms, phenylene or —NH-alkylene-NH— of
2 to 18 carbon atoms, glycidyl, 2,3-dihydroXypropyl, 2 to 18 carbon atoms including 5-amino-1
2-hydroXy or 2-(hydroXymethyl substituted alkyl of 3 aminomethyl-1,3,3-trimethylcycdoheXane and —NH
to 12 carbon atoms Which alkyl is interrupted by Xylylene-NH—;
oXygen, an acyl radical of an aliphatic or unsaturated
R28 is alkyl of 1 to 4 carbon atoms;
aliphatic carboXylic or carbamic acid containing 2 to 18
carbon atoms, an acyl radical of a cycloaliphatic car
boXylic or carbamic acid containing 7 to 12 carbon
atoms, or acyl radical of an aromatic acid containing 7
35
to 15 carbon atoms;
R20 is alkylene of 2 to 18 carbon atoms, a divalent acyl
radical of an aliphatic or unsaturated aliphatic dicar
boXylic or dicarbamic acid containing 2 to 18 carbon
atoms, a divalent acyl radical of a cycloaliphatic dicar
boXylic or dicarbamic acid containing 7 to 12 carbon
or
atoms, or a divalent acyl radical of an aromatic dicar
boXylic acid containing 8 to 15 carbon atoms;
R21, is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of
2 to 6 carbon atoms; 45
R22 is hydrogen, alkyl of 1 to 18 carbon atoms, an acyl
radical of an aliphatic or unsaturated aliphatic carboXy
lic or carbamic acid containing 2 to 18 carbon atoms,
an acyl radical of a cycloaliphatic carboXylic or car
bamic acid containing 7 to 12 carbon atoms, an acyl
radical of an aromatic carboXylic acid containing 7 to
R29 is a straight or branched chain alkyl or —NH-alkyl of
15 carbon atoms, or R4 and R5 together are
1 to 18 carbon atoms or —NH-cycloalkyl of 5 to 8
—(CH2)5CO—, phthaloyl or a divalent acyl radical of
carbon atoms; and
maleic acid;
55 With the further proviso that in formulas (1) and (2), When
R23 is hydrogen, alkyl of 1 to 4 carbon atoms or acyl of
b is 1, E is not methyl, ethyl, 2-propyl or 2-methyl-2
2 to 6 carbon atoms; propyl.
R24 is alkylene of 2 to 18 carbon atoms, a divalent acyl Preferably, G1 and G2 are each methyl.
radical of an aliphatic or unsaturated aliphatic dicar Preferably, in formulas (1) to (28), b is 1 or 2, most
boXylic or dicarbamic acid containing 2 to 18 carbon preferably 1.
atoms, a divalent acyl radical of a cycloaliphatic dicar When b is 1, E—OH and L—OH are respectively a
boXylic or dicarbamic acid containing 7 to 12 carbon carbon-centered radical or diradical formed preferably from
atoms, or a divalent acyl radical of an aromatic dicar 2-methyl-2-propanol, 2-propanol, 2,2-dimethyl-1-propanol,
boXylic acid containing 8 to 15 carbon atoms; 2-methyl-2-butanol, ethanol, 1-propanol, 1-butanol,
R25 is alkoXy of 1 to 18 carbon atoms, alkenyloXy of 2 to 65 1-pentanol, 1-heXanol, 1-nonanol, 1-decanol, 1-dodecanol,
18 carbon atoms, —NHalkyl of 1 to 18 carbon atoms 1-octadecanol, 2-butanol, 2-pentanol, 2-ethyl-1-heXanol,
or —N(alkyl)2 of 2 to 36 carbon atoms, cycloheXanol, cyclooctanol, allyl alcohol, phenethyl alcohol
US 6,271,377 B1
15 16
or 1-phenyl-1-ethanol; most preferably E—OH and L—OH butyl, Which may also be designated as Tl-butylamino, R16
are formed from 2-methyl-2-propanol or cycloheXanol. is hydrogen, acetyl, ethylcarbamoyl, 2,4-bis(dibutylamino)
When b is 2, E—OH and L—OH are respectively a s-triaZinyl, 2,4-bis(diethylamino)-s-triaZinyl, s-triaZinyl
carbon-centered radical or diradical formed preferably from substituted tWice by T1 -butylamino or s-triaZinyl substituted
1,2-ethanediol, 1,2-propanedial, 1,3-propanediol, 1,2 once by diethylamino or dibutylamino and once by
butanediol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1, Tl-butylamino, R17 is dibutylamino, diethylamino,
3-propanediol, 1,2-cycloheXanediol, 1,3-cycloheXanediol or Tl-butylamino or R17 is T3 Where R18 is acetyl or ethylcar
1,4-cycloheXanediol; most preferably E—OH and L—OH bamoyl.
are formed from 1,4-butanediol, 2,2-dimethyl-1,3 Preferably in formula (17), m is 0, R1 is hydrogen or
propanediol, 1,2-cycloheXanediol, 1,3-cycloheXanediol or 10 hydroXymethyl, and R2 is hydrogen; or m is 1, R1 is hydroXy
1,4-cycloheXanediol. or hydroXymethyl, and R2 is hydrogen or methyl.
When b is 3, E—OH and L—OH are respectively a Preferably in formula (19), R2 is hydrogen or dodecyl.
carbon-centered radical or diradical formed from glycerol, Preferably in formula (20), R19 is hydrogen, allyl,
1,1,1-tris(hydroXymethyl)methane, 2-ethyl-2 acryloyl, methacryloyl, octadecanoyl or heXadecanoyl.
(hydroXymethyl-1,3-propanediol, 1,2,4-butanetriol or 1,2,6 15 Preferably in formula (21), R20 is succinyl, glutaryl,
heXanetriol; most preferably E—OH and L—OH are formed adipoyl, sebacoyl, 1,6-heXanedicarbamoyl, or cis- or trans
from glycerol, 1,1,1-tris(hydroXymethyl)methane, 2-ethyl 5-carbamoyl-1-(carbamoylmethyl)-1 ,3,3
2-(hydroXymethyl-1,3-propanediol. trimethylcycloheXane.
Preferably in formulas (29) and (30), —G—O— is Preferably in formula (22), R21 is hydrogen and R22 is
formed from ethanol, phenethyl alcohol, cycloheXanol or hydrogen or butyl; or R21 and R22 together are the divalent
2-methyl-2-propanol (=tert-butyl alcohol). acyl radical of maleic acid.
Preferably in formula (3), m is 0, R1 is hydrogen or Preferably in formula (23), R23 is hydrogen or acetyl, and
hydroXymethyl, and R2 is hydrogen; or m is 1, R1 is hydroXy R24 is ethylene or heXamethylene.
or hydroXymethyl, and R2 is hydrogen, methyl or ethyl. Preferably in formula (24), R25 is ethoXy, 6methyl-1
Preferably in formula (5), R2 is hydrogen or dodecyl. 25 heptyloXy, ethylamino, butylamino or octylamino.
Preferably in formula (6), n is 1 or 2, and When n is 1, R3 Preferably in formula (25), R26 is 1,2-ethanedioXy, 1-4
is allyl, glycidyl, acryloyl, methacryloyl, octadecanoyl, butanedioXy, ethylenediamino or heXamethylenediamino.
heXadecanoyl, tetradecanoyl, methoXycarbonylpropionyl, Preferably in formula (26), R7 and R8 are independently
methoXycarbonylbutyryl, methoXycarbonylpentanoyl or chlorine, octylamino, tert-octylamino, octadecylamino,
methoXycarbonylnonanoyl; or When n is 2, R3 is succinyl, Tl-ethylamino, T1 -butylamino or T1 -odecylamino, and R9 is
glutaryl, adipoyl, sebacoyl, 1,6-heXanedicarbamoyl or cis a divalent nitrogen atom substituted by ethyl, butyl or
or trans-5-carbamoyl-1-(carbamoylmethyl)-1,3,3 dodecyl.
trimethylcyclohexane. Preferably in formula (27), q is 2, 4 or 6, R7 is chlorine,
Preferably in formula (7), p is 1 or 2, and When p is 1, R4 octylamino, octadecylamino, Tl-ethylamino, Tl-butylamino
is hydrogen and R5 is butyl; or R4 and R5 together are the 35 or Tl-dodecylamino, and R10 is hydrogen.
divalent acyl radical of maleic acid; or When p is 2, R4 is Preferably in formula (28), d is 0 or 1, h is 0—2, k is 0 or
hydrogen or acetyl, and R5 is 1,6-heXanediyl. 3, R9 is a divalent oXygen atom or a divalent nitrogen atom
Preferably in formula (8), n is 1 or 2, and When n is 1, R6 substituted by ethyl, butyl or dodecyl, R13 is hydrogen,
is ethoXy, 6-methyl-1-heptyloXy, ethylamino, butylamino or methyl, ethyl, methoXy or ethoXy, and R14 is hydrogen or
octylamino; or When n is 2, R6 is 1,2-ethanedioXy, 1,4 trimethylsilyl.
butanedioXy, ethylenediamino, heXamethylenediamino, or Preferably in formula (29), R27 is ethylene, trimethylene,
4-methyl-1,3-phenylenediamino. tetramethylene, octamethylene, 1,6-diaminoheXane or
Preferably in formula (9), R7 and R8 are independently 5-amino-1-aminomethyl-1,3,3-trimethylcycioheXane; Z is
chlorine, octylamino, tert-octylamino or amino substituted an integer such that the molecular Weight of the compound
by T1 and ethyl, butyl or dodecyl; and R9 is a divalent 45 is 1500—3000 amu, R28 is methyl or ethyl, and G is ethylene,
nitrogen atom substituted by ethyl, butyl or dodecyl. 1,2-cycloheXanediyl, 1,3-cycloheXanediyl, 1,4
Preferably in formula (10), q is 2, 4 or 6, R7 is chlorine, cycloheXanediyl, —CH(C6H5)CH2— or —CH2C(CH3)2—.
octylamino, octadecylamino or amino substituted by T1 and Preferably in formula (30), R29 is pentadecyl, heptadecyl,
ethyl, butyl or dodecyl; and R10 is hydrogen. butylamino or cycloheXylamino.
Preferably in formula (11), n is 3, p is 2, R2 is ethyl, butyl Still more preferred embodiments of the instant invention
or dodecyl; and one of R11 or R12 is T2, and the other is are the compounds of formulas (1) to (30) Where E—OH,
hydrogen. L—OH and G—O— are formed from 2-methyl-2-propanol
Preferably in formula (12), k is 3, R9 is a divalent oXygen (=tert-butyl alcohol) or cycloheXanol.
atom or is a divalent nitrogen atom substituted by ethyl, Most preferably in formula (6), When n is 1, R3 is
butyl or dodecyl, R13 is hydrogen or methyl, and When d is 55 acryloyl, methacrloyl, glycidyl, octadecanoyl,
0,Xis5or6,andWhendis1,Xis3or4. heXadecanoyl, methoXycarbonylpropionyl,
Preferably in formula (13), d is 0 or 1, h is 0—2, k is 0 or methoXycarbonylbutyryl, methoXycarbonylpentanoyl or
3, y is 1—8, R9 is a divalent oXygen atom or a divalent methoXycarbonylnonanoyl; or When n is 2, R3 is succinyl,
nitrogen atom substituted by ethyl, butyl or dodecyl, R13 is glutaryl, adipoyl, sebacoyl, 1,6-heXanedicarbamoyl or cis
hydrogen, methyl, ethyl, methoXy or ethoXy, and R14 is or trans-5-carbamoyl-1-(carbamoylmethyl)-1,3,3
hydrogen or trimethylsilyl. trimethylcycloheXane.
Preferably in formula (14), R9 is a divalent oxygen atom, Most preferably in formula (7), p is 1 or 2, and When p is
R10 is hydrogen or methyl, m is 0 and Z is an integer such 1, R4 is hydrogen and R5 is hydrogen or butyl; or When p is
that the molecular Weight of the compound is 1500—3000 2, R4 is hydrogen, and R5 is 1,6-heXanediyl.
amu. 65 Most preferably in formula (9), R7 is chlorine, octylamino
Preferably in formula (15) q is 6, y is 1—7, R15 is or Tl-butylamino, R8 is chlorine or Tl-butylamino, and R9
tert-octylamino, morpholino, amino substituted by T1 and is a divalent nitrogen atom substituted by butyl.
US 6,271,377 B1
17 18
Most preferably in formula (10), q is 6, R7 is or methyl, and Z is an integer such that the molecular Weight
Tl-butylamino; and R10 is hydrogen. of the compound is 1500—3000 amu.
Most preferably in formula (11), n is 3, p is 2, and one of Especially preferred compounds of formula (15) are those
R11 or R12 is T2, and the other is hydrogen. Where q is 6, y is 1—7, R15 is Tl-butylamino, R16 is
hydrogen, acetyl, ethylcarbamoyl, 2,4-bis(dibutylamino)-s
Most preferably in formula (12), k is 3, R9 is a divalent
triaZinyl, 2,4-bis(diethylamino)-s-triaZinyl, s-triaZinyl sub
oxygen atom, R13 is hydrogen or methyl, and d is 0, X is 5
stituted tWice by Tl-butylamino or s-triaZinyl substituted
or 6, and When d is 1, X is 3 or 4.
Most preferably in formula (13), d is 0 or 1, h is 0—2, k once by diethylamino or dibutylamino and once by
Tl-butylamino, R17 is dibutylamino, diethylamino, or T3
is 0 or 3, y is 1—8, R9 is a divalent oXygen atom, R13 is
hydrogen, methyl, ethyl, methoXy or ethoXy, and R14 is 10 Where R18 is acetyl or ethylcarbamoyl.
hydrogen or trimethylsilyl. Especially preferred compounds of formula (20) are those
Most preferably in formula (15) q is 6, y is 1—7, R15 is Where R19 is hydrogen, octadecanoyl or heXadecanoyl.
Tl-butylamino, R16 is hydrogen, acetyl, ethylcarbamoyl, Especially preferred compounds of formula (21) are those
2,4-bis(dibutylamino)-s-triaZinyl, 2,4-bis(diethylamino)-s Where R20 is succinyl, glutaryl, adipoyl or sebacoyl.
triaZinyl, s-triaZinyl substituted tWice by Tl-butylamino or 15 Especially preferred compound of formula (30) is that
s-triaZinyl substituted once by diethylamino or dibutylamino Where R29 is heptadecyl.
and once by Tl-butylamino, R17 is dibutylamino, The instant invention also pertains to a polymer compo
diethylamino, Tl-butylamino or R17 is T3 Where R18 is sition containing an effective stabiliZing amount of one or
acetyl or ethylcarbamoyl. more compounds selected from the compounds of formula
Most preferably in formula (20), R19 is hydrogen, octa 20 (1) to formula (30) as described above.
decanoyl or heXadecanoyl. Preferably, the organic material is a natural, semi
Most preferably in formula (22), R21, is hydrogen and R22 synthetic or synthetic polymer, especially a thermoplastic
polymer.
is hydrogen or butyl.
Most preferably in formula (23), R23 is hydrogen, and R24 Most preferably, the polymer is a polyole?n, especially a
is heXamethylene. 25 thermoplastic polyole?n useful in automotive coatings and
Most preferably in formula (26), R7 is chlorine, octy applications or a urethane based automotive coating.
lamino or Tl-butylamino, R8 is chlorine or Tl-butylamino, The compounds of this invention eXhibit superior hydro
and R9 is a divalent nitrogen atom substituted by butyl. lytic stability, handling and storage stability as Well as good
Most preferably in formula (27), q is 6, R7 is resistance to eXtractability When present in a stabiliZed
composition.
Tl-butylamino, and R9 is a divalent nitrogen atom substi 30
tuted by butyl. In general polymers Which can be stabiliZed include
Most preferably in formula (29), R27 is ethylene, 1. Polymers of monoole?ns and diole?ns, for eXample
polypropylene, polyisobutylene, polybut-1-ene, poly-4
trimethylene, tetramethylene or octamethylene, Z is an inte
ger such that the molecular Weight of the compound is 1500 methylpent-1-ene, polyisoprene or polybutadiene, as Well as
to 2000 amu, and R28 is methyl. 35 polymers of cycloole?ns, for instance of cyclopentene or
Most preferably in formula (30), R29 is pentadecyl or norbomene, polyethylene (Which optionally can be
heptadecyl. crosslinked), for eXample high density polyethylene
Still more preferred embodiments of the instant invention (HDPE), loW density polyethylene (LDPE), linear loW den
sity polyethylene (LLDPE), branched loW density polyeth
are the compounds of formulas (1) to (30) Where E—OH,
ylene (BLDPE).
L—OH and —G—O— are formed from 2-methyl-2 40
propanol (=tert-butyl alcohol). Polyole?ns, i.e. the polymers of monoole?ns eXempli?ed in
Especially preferred compounds of formula (6) are those the preceding paragraph, preferably polyethylene and
Where n is 1, R3 is acryloyl, methacryloyl, glycidyl, polypropylene, can be prepared by different, and especially
octadecanoyl, heXadecanoyl, methoXycarbonylpropionyl or by the folloWing, methods:
methoXycarbonylbutyryl, and Where n is 2, R3 is succinyl, 45 a) radical polymerisation (normally under high pressure
glutaryl, adipoyl or sebacoyl. and at elevated temperature).
Especially preferred compounds of formula (7) are those b) catalytic polymersation using a catalyst that normally
Where R4 is hydrogen, and When p is 1, R5 is hydrogen or contains one or more than one metal of groups IVb, Vb,
butyl, or When p is 2, R5 is heXamethylene. VIb or VIII of the Periodic Table. These metals usually
Especially preferred compounds of formula (9) are those 50 have one or more than one ligand, typically oXides,
Where R7 is chlorine, octylamino or Tl-butylamino, R8 is halides, alcoholates, esters, ethers, amines, alkyls, alk
Tl-butylamino, and R9 is a divalent nitrogen atom substi enyis and/or aryls that may be either 75- or
tuted by butyl. o-coordinated. These metal compleXes may be in the
Especially preferred compounds of formula (10) are those free form or ?Xed on substrates, typically on activated
Where q is 6, R7 is Tl-butylamino and R10 is hydrogen. 55 magnesium chloride, titanium(ll) chloride, alumina or
Especially preferred compounds of formula (11) are those silicon oXide. These catalysts may be soluble or
Where n is 3, p is 2, one of R11 or R12 is T2 and the other is insoluble in the polymerisation medium. The catalysts
hydrogen. can be used by themselves in the polymerisation or
Especially preferred compounds of formula (12) are those further activators may be used, typically metal alkyls,
Where d is 1, k is 3, X is 3 or 4, R9 is divalent oXygen atom, 60 metal hydrides, metal alkyl halides, metal alkyl oXides
and R13 is methyl. or metal alkyloXanes, said metals being elements of
Especially preferred compounds of formula (13) are those groups Ia, IIa and/or IIIa of the Periodic Table. The
Where k is 3, y is 4—8. R9 is a divalent oXygen atom, R13 is activators may be modi?ed conveniently With further
hydrogen or methyl, d and h are 0, R14 is hydrogen, or d is ester, ether, amine or silyl ether groups. These catalyst
1 and h is 0, and R14 is trimethylsilyl. 65 systems are usually termed Phillips, Standard Oil
Especially preferred compounds of formula (14) are those Indiana, Ziegler (—Natta), TNZ (DuPont), metallocene
Where m is 0, R9 is a divalent oXygen atom, R10 is hydrogen or single site catalysts (SSC).