U.S. patent application number 17/697232 was filed with the patent office on 2022-07-07 for polymeric hollow articles containing chroman-based compounds and made by rotational molding.
The applicant listed for this patent is CYTEC TECHNOLOGY CORP.. Invention is credited to J. Mon Hei ENG, Ram GUPTA, Sari-Beth SAMUELS, Thomas STEELE.
Application Number | 20220212375 17/697232 |
Document ID | / |
Family ID | 1000006200172 |
Filed Date | 2022-07-07 |
United States Patent
Application |
20220212375 |
Kind Code |
A1 |
GUPTA; Ram ; et al. |
July 7, 2022 |
POLYMERIC HOLLOW ARTICLES CONTAINING CHROMAN-BASED COMPOUNDS AND
MADE BY ROTATIONAL MOLDING
Abstract
A stabilizer composition for producing a polymeric hollow
article in a rotomolding process has stabilizing amounts of: (i) at
least one chroman-based compound according to Formula (V):
##STR00001## wherein at least one instance of R.sub.21 is
OR.sub.27, R.sub.27 is COR''' or Si(R.sub.28).sub.3, and R''',
R.sub.22, R.sub.23 R.sub.24, R.sub.25 and R.sub.26 are as defined
herein; (ii) at least one phosphite or phosphonite; and (iii) a
basic co-additive selected from alkali metal or alkaline metal
salts of higher fatty acids. A polymeric hollow article is made by
a process comprising: a) filling a mold with a polyolefin and a
stabilizing amount of the stabilizer composition described
herewith; b) rotating the mold around at least one axis while
heating the mold in an oven, thereby fusing the composition and
spreading it to the walls of the mold; c) cooling the mold; and d)
opening the mold to remove the resulting polymeric hollow
article.
Inventors: |
GUPTA; Ram; (Stamford,
CT) ; SAMUELS; Sari-Beth; (Ramsey, NJ) ;
STEELE; Thomas; (Milford, CT) ; ENG; J. Mon Hei;
(Wilton, CT) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CYTEC TECHNOLOGY CORP. |
Princeton |
NJ |
US |
|
|
Family ID: |
1000006200172 |
Appl. No.: |
17/697232 |
Filed: |
March 17, 2022 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13323173 |
Dec 12, 2011 |
11312043 |
|
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17697232 |
|
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61422255 |
Dec 13, 2010 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08K 5/1545 20130101;
C08L 23/0815 20130101; B29C 41/04 20130101; C08K 5/00 20130101;
C08K 5/005 20130101; C08K 5/34 20130101; C08K 5/51 20130101; C07D
311/72 20130101; B29K 2023/0625 20130101; Y02P 20/10 20151101 |
International
Class: |
B29C 41/04 20060101
B29C041/04; C08K 5/00 20060101 C08K005/00; C08K 5/34 20060101
C08K005/34; C08K 5/1545 20060101 C08K005/1545; C08L 23/08 20060101
C08L023/08; C08K 5/51 20060101 C08K005/51; C07D 311/72 20060101
C07D311/72 |
Claims
1. A polymeric hollow article made by a process comprising: a)
filling a mold with a polyolefin and a stabilizing amount of a
stabilizer composition, wherein the stabilizer composition
comprises: (i) at least one chroman-based compound according to
Formula (V): ##STR00036## wherein R.sub.21 is present at from 1 to
4 positions of the aromatic portion of Formula (V) and in each
instance is independently chosen from: C.sub.1-C.sub.12
hydrocarbyl; NR'R'', wherein each of R' and R'' is independently
chosen from H or C.sub.1-C.sub.12 hydrocarbyl; or OR.sub.27,
wherein R.sub.27 is chosen from C.sub.1-C.sub.12 hydrocarbyl,
COR''' or Si(R.sub.28).sub.3, wherein R''' is chosen from H or
C.sub.1-C.sub.20 hydrocarbyl and R.sub.28 is chosen from
C.sub.1-C.sub.12 hydrocarbyl or alkoxy; and wherein at least one
instance of R.sub.21 is OR.sub.27; R.sub.22 is chosen from H or
C.sub.1-C.sub.12 hydrocarbyl; R.sub.23 is chosen from H or
C.sub.1-C.sub.20 hydrocarbyl; each of R.sub.24-R.sub.25 is
independently chosen from H, C.sub.1-C.sub.12 hydrocarbyl or
OR'''', wherein R'''' is chosen from H or C.sub.1-C.sub.12
hydrocarbyl; and R.sub.26 is H or a bond which together with
R.sub.25 forms .dbd.O; (ii) at least one phosphite or phosphonite;
and (iii) a basic co-additive selected from alkali metal or
alkaline metal salts of higher fatty acids; b) rotating the mold
around at least one axis while heating the mold in an oven, thereby
fusing the composition and spreading it to the walls of the mold;
c) cooling the mold; and d) opening the mold to remove the
resulting product, thereby producing the polymeric hollow
article.
2. A polymeric hollow article according to claim 1, wherein the at
least one phosphite or phosphonite is chosen from: (i) a compound
according to Formulas (1)-(7): ##STR00037## in which the indices
are integral and n is 2, 3 or 4; p is 1 or 2; q is 2 or 3; y is 1,
2 or 3; and z is 1 to 6; A.sub.1, if n or q is 2, is
C.sub.2-C.sub.18 alkylene; C.sub.2-C.sub.12 alkylene interrupted by
oxygen, sulfur or --NR.sub.4--; a radical of the formula
##STR00038## or phenylene; A.sub.1, if n or q is 3, is a trivalent
radical of the formula C.sub.rH.sub.2r-1; wherein r is an integer
from 4 to 12; A.sub.1, if n is 4, is ##STR00039## B is a direct
bond, --CH.sub.2--, --CHR.sub.4--, --CR.sub.1R.sub.4--, sulfur,
C.sub.5-C.sub.7 cycloalkylidene, or cyclohexylidene which is
substituted by from 1 to 4 C.sub.1-C.sub.4 alkyl radicals in
position 3, 4 and/or 5; D.sub.1, if p is 1, is C.sub.1-C.sub.4
alkyl and, if p is 2, is --CH.sub.2OCH.sub.2--; D.sub.2, if p is 1,
is C.sub.1-C.sub.4 alkyl; E, if y is 1, is C.sub.1-C.sub.18 alkyl,
--OR.sub.1 or halogen; E, if y is 2, is --O-A.sub.2-O--, wherein
A.sub.2 is as defined for A.sub.1 when n is 2; E, if y is 3, is a
radical of the formula R.sub.4C(CH.sub.2O--).sub.3 or
N(CH.sub.2CH.sub.2O--).sub.3; Q is the radical of an at least
z-valent mono- or poly-alcohol or phenol, this radical being
attached via the oxygen atom of the OH group of the mono- or
poly-alcohol or phenol to the phosphorus atom; R.sub.1, R.sub.2 and
R.sub.3 independently of one another are C.sub.1-C.sub.18 alkyl
which is unsubstituted or substituted by halogen, --COOR.sub.4,
--CN or --CONR.sub.4R.sub.4; C.sub.2-C.sub.18 alkyl interrupted by
oxygen, sulfur or --NR.sub.4--; C.sub.7-C.sub.9 phenylalkyl;
C.sub.5-C.sub.12 cycloalkyl, phenyl or naphthyl; naphthyl or phenyl
substituted by halogen, 1 to 3 alkyl radicals or alkoxy radicals
having a total of 1 to 18 carbon atoms or by C.sub.7-C.sub.9
phenylalkyl; or a radical of the formula ##STR00040## in which m is
an integer from the range 3 to 6; R.sub.4 is hydrogen,
C.sub.1-C.sub.8 alkyl, C.sub.5-C.sub.12 cycloalkyl or
C.sub.7-C.sub.9 phenylalkyl, R.sub.5 and R.sub.6 independently of
one another are hydrogen, C.sub.1-C.sub.8 alkyl or C.sub.5-C.sub.6
cycloalkyl, R.sub.7 and R.sub.8, if q is 2, independently of one
another are C.sub.1-C.sub.4 alkyl or together are a
2,3-dehydropentamethylene radical; R.sub.7 and R.sub.8, if q is 3,
are methyl; each instance of R.sub.14 is independently hydrogen,
C.sub.1-C.sub.9 alkyl or cyclohexyl; each instance of R.sub.15 is
independently hydrogen or methyl; X and Y are each a direct bond or
oxygen; Z is a direct bond, methylene, --C(R.sub.16).sub.2-- or
sulfur; and R.sub.16 is C.sub.1-C.sub.8 alkyl; (ii) a
trisarylphosphite according to Formula 8: ##STR00041## wherein
R.sub.17 is a substituent that is present at from 0 to 5 positions
of the aromatic portion of Formula (8) and in each instance is
independently chosen from C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20
cycloalkyl, C.sub.4-C.sub.20 alkyl cycloalkyl, C.sub.6-C.sub.10
aryl or C.sub.7-C.sub.20 alkylaryl; or (iii) mixtures of (i) and
(ii).
3. A polymeric hollow article according to claim 2, wherein the
phosphite or phosphonite is chosen from triphenyl phosphite;
diphenyl alkyl phosphites; phenyl dialkyl phosphites; trilauryl
phosphite; trioctadecyl phosphite; distearyl pentaerythritol
phosphite; tris(2,4-di-t-butylphenyl) phosphite; tris(nonylphenyl)
phosphite; a compound of formulae (A), (B), (C), (D), (E), (F),
(G), (H), (J), (K) or (L): ##STR00042## ##STR00043##
2-butyl-2-ethyl-1,3-propanediol 2,4,6-tri-t-butylphenol phosphite;
bis-(2,6-di-t-butyl-4-methlphenyl) pentaerythritol diphosphite;
2-butyl-2-ethyl-1,3-propanediol 2,4-di-cumylphenol phosphite;
2-butyl-2-ethyl-1,3-propanediol 4-methyl-2,6-di-t-butylphenol
phosphite or bis-(2,4,6-tri-t-butyl-phenyl) pentaerythritol
diphosphite.
4. A polymeric hollow article according to claim 2, wherein the at
least one phosphite or phosphonite is chosen from
tris(2,4-di-t-butylphenyl)phosphite (IRGAFOS.RTM. 168);
bis(2,4-dicumylphenyl)pentaerythritol diphosphite (DOVERPHOS.RTM.
S9228) or
tetrakis(2,4-di-t-butylphenyl)4,4'-biphenylene-diphosphonite
(IRGAFOS.RTM. P-EPQ).
5. A polymeric hollow article according to claim 1, wherein the
stabilizer composition further comprises at least one hindered
phenol.
6. A polymeric hollow article according to claim 5, wherein the at
least one hindered phenol comprises a molecular fragment according
to one or more of Formula (IVa), (IVb), or (IVc): ##STR00044##
wherein R.sub.18 of Formula (IVa), (IVb), or (IVc) is independently
chosen from hydrogen or a C.sub.1-4 hydrocarbyl; each of R.sub.19
and R.sub.20 of Formula (IVa), (IVb), or (IVc) is independently
chosen from hydrogen or a C.sub.1-C.sub.20 hydrocarbyl; and
R.sub.37 of Formula (IVa), (IVb), or (IVc) is independently chosen
from a C.sub.1-C.sub.12 hydrocarbyl.
7. A polymeric hollow article according to claim 6, wherein
R.sub.18 and R.sub.37 are chosen from methyl or t-butyl.
8. A polymeric hollow article according to claim 6, wherein the at
least one hindered phenol compound is chosen from
(1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6--
(1H,3H,5H)-trione;
1,1,3-tris(2'-methyl-4'-hydroxy-5'-t-butylphenyl)butane;
triethylene glycol
bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate];
4,4'-thiobis(2-t-butyl-5-methylphenol); 2,2'-thiodiethylene
bis[3-(3-t-butyl-4-hydroxyl-5-methylphenyl)propionate]; octadecyl
3-(3'-t-butyl-4'-hydroxy-5'-methylphenyl)propionate;
tetrakismethylene(3-t-butyl-4-hydroxy-5-methylhydrocinnamate)methane;
N,N'-hexamethylene
bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionamide];
di(4-t-butyl-3-hydroxy-2,6-dimethyl benzyl) thiodipropionate;
octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate; or mixtures
thereof.
9. A polymeric hollow article according to claim 1, wherein
R.sub.21 is present in at least one instance as OR.sub.27.
10. A polymeric hollow article according to claim 9, wherein
R.sub.21 is present in at least three instances and is chosen from
OR.sub.27 or methyl.
11. A polymeric hollow article according to claim 9, wherein
R.sub.23 is a C.sub.1-C.sub.18 hydrocarbyl.
12. A polymeric hollow article according to claim 1, wherein the
chroman-based compound is vitamin E acetate according to Formula
(Va) ##STR00045## wherein R.sub.21 is --OC(O)CH.sub.3.
13. A polymeric hollow article according to claim 1, wherein the
chroman-based compound comprises two or more compounds according to
Formula (V).
14. A polymeric hollow article according to claim 1, wherein the
chroman-based compound is present from 0.001% to 5.0% by weight of
the weight of the polyolefin.
15. A polymeric hollow article according to claim 14, wherein the
chroman-based compound is present from 0.01% to 1.0% by weight of
the weight of the polyolefin.
16. A polymeric hollow article according to claim 1, wherein the
polyolefin is chosen from: (i) polymers of monoolefins chosen from
polypropylene, polyisobutylene, polybut-1-ene, or
poly-4-methylpent-1-ene; (ii) polymers of diolefins chosen from
polyisoprene or polybutadiene; (iii) polymers of cycloolefins
chosen from cyclopentene or norbornene; (iv) polyethylene chosen
from optionally crosslinked polyethylene, high density polyethylene
(HDPE), high density and high molecular weight polyethylene
(HDPE-HMW), high density and ultrahigh molecular weight
polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low
density polyethylene (LDPE), linear low density polyethylene
(LLDPE), very low density polyethylene (VLDPE), or ultralow density
polyethylene (ULDPE); (v) copolymers of the monoolefins, diolefins,
or cycloolefins of any of (i) to (iv); or vi) mixtures of any of
(i) to (v).
17. A polymeric hollow article according to claim 16, wherein the
polyolefin is at least one of linear low density polyethylene
(LLDPE), medium density polyethylene (MDPE), high density
polyethylene (HDPE), or polypropylene.
18. A polymeric hollow article according to claim 1, wherein the
stabilizer composition further comprises a light stabilizer chosen
from hindered amine light stabilizers, hindered hydroxyl benzoates,
nickel phenolates, ultraviolet light stabilizers, or mixtures
thereof, in an amount effective to stabilize the polymer
composition against the degradative effects of visible and/or
ultraviolet light radiation.
19. A polymeric hollow article according to claim 18, wherein the
light stabilizer is a hindered amine light stabilizer comprising a
molecular fragment according to: (i) Formula (VI): ##STR00046##
wherein R.sub.31 is chosen from hydrogen, OH, C.sub.1-C.sub.20
hydrocarbyl, --CH.sub.2CN, C.sub.1-C.sub.12 acyl or
C.sub.1-C.sub.18 alkoxy; R.sub.38 is chosen from hydrogen or
C.sub.1-C.sub.8 hydrocarbyl; and each of R.sub.29, R.sub.30,
R.sub.31, and R.sub.32 is independently chosen from a
C.sub.1-C.sub.20 hydrocarbyl; or R.sub.60 and R.sub.61 and/or
R.sub.63 and R.sub.64 taken together with the carbon to which they
are attached form a C.sub.5-C.sub.10 cycloalkyl; or (ii) Formula
(VIa) ##STR00047## wherein m is an integer from 1 to 2; R.sub.39 is
chosen from hydrogen, OH, C.sub.1-C.sub.20 hydrocarbyl,
--CH.sub.2CN, C.sub.1-C.sub.12 acyl, or C.sub.1-C.sub.18 alkoxy;
and each of G.sub.1-G.sub.4 is independently a C.sub.1-C.sub.20
hydrocarbyl.
20. A polymeric hollow article according to claim 19, wherein the
hindered amine light stabilizer is chosen from
bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate;
bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl
3,5-di-tert-butyl-4-hydroxybenzylmalonate; a condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid; 2,2,6,6-tetramethylpiperidin-4-yl stearate;
2,2,6,6-tetramethylpiperidin-4-yl dodecanate;
1,2,2,6,6-pentamethylpiperidin-4-yl stearate;
1,2,2,6,6-pentamethylpiperidin-4-yl dodecanate; a condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine;
tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate;
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylat-
e; 4-benzoyl-2,2,6,6-tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-bu-
tylbenzyl)malonate;
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate; a condensate
of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine
and 4-morpholino-2,6-dichloro-1,3,5-triazine; a condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane; a condensate of
2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis-(3-aminopropylamino)ethane;
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d-
ione;
3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;
3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5--
dione;
3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-di-
one; a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine; a condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; a condensate of
1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine
and 4-butylamino-2,2,6,6-tetramethylpiperidine;
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane;
oxo-piperanzinyl-triazines; a reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
and epichlorohydrin; tetrakis(2,2,6,6-tetramethyl-4-piperidyl)
butane-1,2,3,4-tetracarboxylate; 1,2,3,4-butanetetracarboxylic
acid, tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl)ester;
1,2,3,4-butanetetracarboxylic acid,
1,2,2,6,6-pentamethyl-4-piperdinyl tridecyl ester;
1,2,3,4-butanetetracarboxylic acid,
2,2,6,6-tetramethyl-4-piperidinyl tridecyl ester;
1,2,3,4-butanetetracarboxylic acid, polymer with
2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]-undecane-3,9-diethanol,1,-
2,2,6,6-pentamethyl-4-piperdinyl ester;
1,2,3,4-butanetetracarboxylic acid, polymer with
2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]-undecane-3,9-diethanol,
2,2,6,6-tetramethyl-4-piperdinyl ester;
bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate;
1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-piperdinol;
1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperi-
dine;
1-(4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-octadec-
anoyloxy-2-methylpropane;
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperdinol; a reaction
product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperdinol and
dimethylsuccinate;
2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one;
the ester of 2,2,6,6-tetramethyl-4-piperidinol with higher fatty
acids;
3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione;
1H-Pyrrole-2,5-dione, 1-octadecyl-, polymer with
(1-methylethenyl)benzene and
1-(2,2,6,6-tetramethyl-4-piperidinyl)-1H-pyrrole-2,5-dione;
piperazinone,
1,1',1''-[1,3,5-triazine-2,4,6-triyltris[(cyclohexylimino)-2,1-ethanediyl-
]]tris[3,3,5,5-tetramethyl-; piperazinone,
1,1',1''-[1,3,5-triazine-2,4,6-triyltris[(cyclohexylimino)-2,1-ethanediyl-
]]tris[3,3,4,5,5-pentamethyl-; the reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
and epichlorohydrin; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; the condensate of
1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine
and 4-butylamino-2,2,6,6-tetramethylpiperidine; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine; the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane; the condensate of
2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis-(3-aminopropylamino)ethane;
2-[(2-hydroxyethyl)amino]-4,6-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylp-
iperidin-4-yl)butylamino-1,3,5-triazine; propanedioic acid,
[(4-methoxyphenyl)-methylene]-bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)
ester;
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracar-
boxylate; benzenepropanoic acid,
3,5-bis(1,1-dimethylethyl)-4-hydroxy-,
1-[2-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]ethyl]--
2,2,6,6-tetramethyl-4-piperidinyl ester;
N-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N'-dodecyloxalamide;
tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate;
1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid,
bis(1,2,2,6,6-pentamethyl-4-piperidinyl):
1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid,
bis(2,2,6,6-tetramethyl-4-piperidinyl); the condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine;
1,2,3,4-butanetetracarboxylic acid,
1,2,2,6,6-pentamethyl-4-piperidinyl tridecyl ester;
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylat-
e; 1,2,3,4-butanetetracarboxylic acid,
2,2,6,6-tetramethyl-4-piperidinyl tridecyl ester;
tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxyl-
ate; mixture of
2,2,4,4-tetramethyl-21-oxo-7-oxa-3.20-diazaspiro(5.1.11.2)-heneicosane-20-
-propanoic acid-dodecylester and
2,2,4,4-tetramethyl-21-oxo-7-oxa-3.20-diazaspiro(5.1.11.2)-heneicosane-20-
-propanoic acid-tetradecylester;
1H,4H,5H,8H-2,3a,4a,6,7a,8a-hexaazacyclopenta[def]fluorene-4,8-dione,
hexahydro-2,6-bis(2,2,6,6-tetramethyl-4-piperidinyl)-;
polymethyl[propyl-3-oxy(2',2',6',6'-tetramethyl-4,4'-piperidinyl)]siloxan-
e;
polymethyl[propyl-3-oxy(1',2',2',6',6'-pentamethyl-4,4'-piperidinyl)]si-
loxane; copolymer of methylmethacrylate with ethyl acrylate and
2,2,6,6-tetramethylpiperidin-4-yl acrylate; copolymer of mixed
C.sub.20 to C.sub.24 alpha-olefins and
(2,2,6,6-tetramethylpiperidin-4-yl)succinimide;
1,2,3,4-butanetetracarboxylic acid, polymer with
.beta.,.beta.,.beta.',.beta.'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]unde-
cane-3,9-diethanol, 1,2,2,6,6-pentamethyl-4-piperidinyl ester;
1,2,3,4-butanetetracarboxylic acid, polymer with
.beta.,.beta.,.beta.',.beta.'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]unde-
cane-3,9-diethanol, 2,2,6,6-tetramethyl-4-piperidinyl ester
copolymer; 1,3-benzenedicarboxamide,
N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl;
1,1'-(1,10-dioxo-1,10-decanediyl)-bis(hexahydro-2,2,4,4,6-pentamethylpyri-
midine; ethane diamide,
N-(1-acetyl-2,2,6,6-tetramethylpiperidinyl)-N'-dodecyl; formamide,
N,N'-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl);
D-glucitol,
1,3:2,4-bis-O-(2,2,6,6-tetramethyl-4-piperidinylidene)-;
2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane;
propanamide,
2-methyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)-2-[(2,2,6,6-tetramethyl-4--
piperidinyl)amino]-;
7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-20-propanoic acid,
2,2,4,4-tetramethyl-21-oxo-, dodecyl ester;
N-(2,2,6,6-tetramethylpiperidin-4-yl)-.beta.-aminopropionic acid
dodecyl ester;
N-(2,2,6,6-tetramethylpiperidin-4-yl)-N'-aminooxalamide;
propanamide,
N-(2,2,6,6-tetramethyl-4-piperidinyl)-3-[(2,2,6,6-tetramethyl-4-piperidin-
yl)amino]-; mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione;
3-dodecyl-1-(1-ethanoyl-2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-
-dione; bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl
3,5-di-tert-butyl-4-hydroxybenzylmalonate;
tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate;
1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone);
4-benzoyl-2,2,6,6-tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-bu-
tylbenzyl)malonate;
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate;
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d-
ione;
3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;
3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5--
dione;
3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-di-
one; a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane;
1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid,
bis(2,2,6,6-tetramethyl-4-piperidinyl) and
1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid,
bis(1,2,2,6,6-pentamethyl-4-piperidinyl);
N.sup.1-(p-hydroxyethyl)3,3-pentamethylene-5,5-dimethylpiperazin-2-one;
N.sup.1-tert-octyl-3,3,5,5-tetramethyl-diazepin-2-one;
N.sup.1-tert-octyl-3,3-pentamethylene-5,5-hexamethylene-diazepin-2-one;
N.sup.1-tert-octyl-3,3-pentamethylene-5,5-dimethylpiperazin-2-one;
trans-1,2-cyclohexane-bis-(N.sup.1-5,5-dimethyl-3,3-pentamethylene-2-pipe-
razinone;
trans-1,2-cyclohexane-bis-(N.sup.1-3,3,5,5-dispiropentamethylene-
-2-piperazinone);
N.sup.1-isopropyl-1,4-diazadispiro-(3,3,5,5)pentamethylene-2-piperazinone-
;
N.sup.1-isopropyl-1,4-diazadispiro-3,3-pentamethylene-5,5-tetramethylene-
-2-piperazinone;
N.sup.1-isopropyl-5,5-dimethyl-3,3-pentamethylene-2-piperazinone;
trans-1,2-cyclohexane-bis-N.sup.1-(dimethyl-3,3-pentamethylene-2-piperazi-
none);
N.sup.1-octyl-5,5-dimethyl-3,3-pentamethylene-1,4-diazepin-2-one;
N.sup.1-octyl-1,4-diazadispiro-(3,3,5,5)pentamethylene-1,5-diazepin-2-one-
; or mixtures thereof.
21. A polymeric hollow article according to claim 18, wherein the
light stabilizer is an ultraviolet light absorber chosen from a
2-hydroxybenzophenone, a 2-(2'-hydroxyphenyl)benzotriazole, a
2-(2'-hydroxyphenyl)-1,3,5-triazine, or mixtures thereof.
22. A polymeric hollow article according to claim 21, wherein the
ultraviolet light absorber is a 2-(2'-hydroxyphenyl)-1,3,5-triazine
according to Formula (VII): ##STR00048## wherein each of R.sub.34
and R.sub.35 is independently chosen from optionally substituted
C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.10 hydrocarbyl-substituted
amino, C.sub.1-C.sub.10 acyl or C.sub.1-C.sub.10 alkoxyl; and
R.sub.36 is present at from 0 to 4 positions of the phenoxy portion
of Formula (VII) and in each instance is independently chosen from
hydroxyl, C.sub.1-C.sub.12 hydrocarbyl, C.sub.1-C.sub.12 alkoxyl,
C.sub.1-C.sub.12 alkoxyester, or C.sub.1-C.sub.12 acyl.
23. A polymeric hollow article according to claim 22, wherein the
2-(2'-hydroxyphenyl)-1,3,5-triazine is chosen from
4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine
(CYASORB.RTM. 1164 available from Cytec Industries Inc.);
4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine;
2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;
2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazi-
ne;
2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dime-
thylphenyl)-s-triazine;
2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine-
;
2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazi-
ne; 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine;
2,4-bis(4-biphenylyl)-6-[2-hydroxy-4-[(octyloxycarbonyl)ethylideneoxy]phe-
nyl]-s-triazine;
2,4-bis(4-biphenylyl)-6-[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-s-triazine;
2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-h-
ydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine;
2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4(-3-benzyloxy-2-hydroxypropylox-
y)phenyl]-s-triazine;
2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triaz-
ine;
2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy-2-hydroxypropy-
loxy)-5-.alpha.-cumylphenyl]-s-triazine;
methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hy-
droxypropoxy)phenyl]-s-triazine}; methylene bridged dimer mixture
bridged in the 3:5', 5:5' and 3:3' positions in a 5:4:1 ratio;
2,4,6-tris(2-hydroxy-4-isooctyloxycarbonyliso-propylideneoxy-phenyl)-s-tr-
iazine;
2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-.alpha.-cumy-
lphenyl)-s-triazine;
2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyl-
oxy)phenyl]-s-triazine;
2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)-phenyl]-s-tria-
zine; mixture of
4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropox-
y)phenyl)-s-triazine and
4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-tridecyloxy-2-hydroxypropo-
xy)phenyl)-s-triazine (Tinuvin.RTM. 400 available from Ciba
Specialty Chemicals Corp.);
4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4(3-(2-ethylhexyloxy)-2-hydroxy-
propoxy)-phenyl)-s-triazine;
4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine; or mixtures
thereof.
24. A polymeric hollow article according to claim 18, wherein the
light stabilizer is a hindered amine light stabilizer and an
ultraviolet light absorber.
25. A polymeric hollow article according to claim 1, wherein the
stabilizer composition further comprises at least one of: (i) a
hydroxylamine according to Formula (VIII): ##STR00049## wherein
T.sub.1 is chosen from an optionally substituted C.sub.1-C.sub.36
hydrocarbyl, C.sub.5-C.sub.12 cycloalkyl, or C.sub.7-C.sub.9
aralkyl; and T.sub.2 is chosen from hydrogen or T.sub.1; or (ii) a
tertiary amine oxide according to Formula (IX): ##STR00050##
wherein each of W.sub.1 and W.sub.2 is independently a
C.sub.6-C.sub.36 hydrocarbyl chosen from straight or branched chain
C.sub.6-C.sub.36 alkyl, C.sub.6-C.sub.12 aryl, C.sub.7-C.sub.36
aralkyl, C.sub.7-C.sub.36 alkaryl, C.sub.6-C.sub.36 cycloalkyl,
C.sub.6-C.sub.36 alkcycloalkyl, or C.sub.6-C.sub.36
cycloalkylalkyl; W.sub.3 is a C.sub.1-C.sub.36 hydrocarbyl is
chosen from straight or branched chain C.sub.1-C.sub.36 alkyl,
C.sub.6-C.sub.12 aryl, C.sub.7-C.sub.36 aralkyl, C.sub.7-C.sub.36
alkylaryl, C.sub.5-C.sub.36 cycloalkyl, C.sub.6-C.sub.36
alkylcycloalky, and C.sub.6-C.sub.36 cycloalkylalkyl; with the
proviso that at least one of W.sub.1, W.sub.2 or W.sub.3 contains a
R carbon-hydrogen bond; and wherein said alkyl, aralkyl, alkaryl,
cycloalkyl, alkcycloalkyl and cycloalkylalkyl groups of W.sub.1,
W.sub.2 and W.sub.3 may be interrupted by from one to sixteen
groups chosen from --O--, --S--, --SO--, --SO.sub.2--, --COO--,
--OCO--, --CO--, --NW.sub.4--, --CONW.sub.4-- or --NW.sub.4CO--, or
wherein said alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and
cycloalkylalkyl groups of W.sub.1, W.sub.2 and W.sub.3 are
substituted with from one to sixteen groups chosen from --OW.sub.4,
--SW.sub.4, --COOW.sub.4, --OCOW.sub.4, --COW.sub.4,
--N(W.sub.4).sub.2, --CON(W.sub.4).sub.2, --NW.sub.4COW.sub.4 and
5- and 6-membered rings containing the group
--C(CH.sub.3)(CH.sub.2R.sub.x)NL(CH.sub.2R.sub.x)(CH.sub.3)C--; and
wherein W.sub.4 is chosen from hydrogen or C.sub.1-C.sub.8 alkyl;
R.sub.x is chosen from hydrogen or methyl; and L is chosen from
C.sub.1-C.sub.30 alkyl, --C(O)R or --OR, wherein R is
C.sub.1-C.sub.30 straight or branched chain alkyl; or wherein said
alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and
cycloalkylalkyl groups of W.sub.1, W.sub.2 and W.sub.3 are both
interrupted and substituted by any of the groups mentioned above;
or wherein said aryl groups of W.sub.1, W.sub.2 and W.sub.3 are
substituted with from one to three substituents independently
chosen from halogen, C.sub.1-C.sub.8 alkyl or C.sub.1-C.sub.8
alkoxy; or (iii) mixtures of (i) and (ii).
26. A polymeric hollow article according to claim 25, wherein the
hydroxylamine according to Formula (VIII) is an
N,N-dihydrocarbylhydroxylamine wherein each of T.sub.1 and T.sub.2
is independently chosen from benzyl, ethyl, octyl, lauryl, dodecyl,
tetradecyl, hexadecyl, heptadecyl or octadecyl; or wherein each of
T.sub.1 and T.sub.2 is the alkyl mixture found in hydrogenated
tallow amine.
27. A polymeric hollow article according to claim 25, wherein the
hydroxylamine according to Formula (VIII) is an
N,N-dihydrocarbylhydroxylamine chosen from
N,N-dibenzylhydroxylamine; N,N-diethylhydroxylamine;
N,N-dioctylhydroxylamine; N,N-dilaurylhydroxylamine;
N,N-didodecylhydroxylamine; N,N-ditetradecylhydroxylaamine;
N,N-dihexadecylhydroxylamine; N,N-dioctadecylhydroxylamine;
N-hexadecyl-N-tetradecylhydroxylamine;
N-hexadecyl-N-heptadecylhydroxylamine;
N-hexadecyl-N-octadecylhydroxylamine;
N-heptadecyl-N-octadecylhydroxylamine; N,N-di(hydrogenated
tallow)hydroxylamine; or mixtures thereof.
28. A polymeric hollow article according to claim 1, wherein the
hollow article further comprises at least one co-additive chosen
from nucleating agents, fillers, reinforcing agents, polymer
additives or mixtures thereof.
29. A polymeric hollow article according to claim 16, wherein the
polyolefin is at least one of linear low density polyethylene
(LLDPE), medium density polyethylene (MDPE), high density
polyethylene (HDPE), or polypropylene.
30. A polymeric hollow article according to claim 1, wherein the
basic co-additive (iii) is at least one of calcium stearate, zinc
stearate, magnesium behenate, magnesium stearate, sodium
ricinoleate or potassium palmitate.
31. A polymeric hollow article according to claim 29, wherein the
polyolefin, chroman-based compound, phosphite or phosphonite, and
at least one basic co-additive, and amounts of the chroman-based
compound, phosphite or phosphonite, and at least one basic
co-additive are selected so that the polyolefin remains stable and
retains its optimal mechanical and/or physical properties over a
longer period of time in the oven, even in the absence of a
sterically hindered amine light stabilizer (HALS).
32. A polymeric hollow article according to claim 29, wherein the
polyolefin, chroman-based compound, phosphite or phosphonite, and
at least one basic co-additive, and amounts of the chroman-based
compound, phosphite or phosphonite compound, and at least one basic
co-additive are selected so that at least one of the following
results are obtained in a rotational molding operation employed to
produce the polymeric hollow article, even in the absence of
sterically hindered amine light stabilizers (HALS): a maximum mean
failure energy (MFE) of the polymeric article is reached at a
shorter time interval; a higher MFE of the polymeric article is
retained over a longer heating time; or a processing window is
enlarged to a peak internal air temperature (PIAT) of up to
452.degree. F. with yellowness index of the article remaining
substantially unchanged up to a PIAT of 452.degree. F.
33. A polymeric hollow article according to claim 32, wherein the
results are obtained even in the absence of antistatic agents.
34. A stabilizer composition for use in producing a polymeric
hollow article in a rotomolding process, the stabilizer composition
comprising a stabilizing amounts of: (i) at least one chroman-based
compound according to Formula (V): ##STR00051## wherein R.sub.21 is
present at from 0 to 4 positions of the aromatic portion of Formula
(V) and in each instance is independently chosen from:
C.sub.1-C.sub.12 hydrocarbyl; NR'R'', wherein each of R' and R'' is
independently chosen from H or C.sub.1-C.sub.12 hydrocarbyl; or
OR.sub.27, wherein R.sub.27 is chosen from C.sub.1-C.sub.12
hydrocarbyl, COR''', or Si(R.sub.28).sub.3, wherein R''' is chosen
from H or C.sub.1-C.sub.20 hydrocarbyl; and wherein R.sub.28 is
chosen from C.sub.1-C.sub.12 hydrocarbyl or alkoxy; R.sub.22 is
chosen from H or C.sub.1-C.sub.12 hydrocarbyl; R.sub.23 is chosen
from H or C.sub.1-C.sub.20 hydrocarbyl; each of R.sub.24-R.sub.25
is independently chosen from H, C.sub.1-C.sub.12 hydrocarbyl or
OR'''', wherein R'''' is chosen from H or C.sub.1-C.sub.12
hydrocarbyl; and R.sub.26 is H or a bond which together with
R.sub.25 forms .dbd.O; (ii) at least one phosphite or phosphonite;
and (iii) a basic co-additive selected from alkali metal or
alkaline metal salts of higher fatty acids.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. application Ser.
No. 13/323,173 filed Dec. 12, 2011 (allowed), which claims priority
benefit of U.S. Provisional Application No. 61/422,255 filed Dec.
13, 2010 (expired), each of which is incorporated herein by
reference in its entirety. This application is also related in
subject matter to U.S. Pat. No. 11,267,951 issued Mar. 8, 2022, and
U.S. application Ser. No. 17/591,781 filed Feb. 3, 2022.
BACKGROUND OF THE INVENTION
Technical Field
[0002] The present invention generally relates to the production of
hollow articles using the rotational molding process. More
particularly, the present invention relates to the additives
described hereinbelow and their use in such processes to improve
molding cycle time (i.e., reducing curing time) while maintaining
process stability over a broader range of temperatures.
Description of the Related Art
[0003] Rotational molding, or rotomolding, is a high-temperature,
low-pressure forming process that uses heat and biaxial rotation to
produce hollow, one-piece parts, typically made of plastic. Such
plastic hollow parts typically made by a rotomolding process
include, for example, gasoline containers, garbage cans,
agricultural storage vessels, septic tanks, toys, and sporting
goods such as kayaks.
[0004] The process is undertaken by loading a charge of finely
divided plastic resin into the mold "shell", then rotating the mold
(usually, on two axes) while heating it to a temperature above the
melting point of the plastic resin. The melted plastic flows
through the mold cavity under the forces caused by the rotation of
the apparatus. The rotation continues for sufficient time to allow
the molten plastic to cover the surface of the mold. The mold is
then cooled to permit the plastic to freeze into a solid. The final
stage of the molding cycle is the removal of the part from the
rotomolding machine.
[0005] The time required to complete the molding cycle is a
function of the bulk properties of the plastic which is being
molded. For example, it is recognized by those skilled in the art
that the plastic resin which is charged into the mold is preferably
finely divided (i.e. ground into powder) and has a high bulk
density and a narrow particle size distribution to facilitate the
"free flow" of the resin.
[0006] It will also be appreciated that the physical properties of
the rotomolded part are influenced by the use of a proper molding
cycle time with "undercooked" parts having poor strength properties
and "overcooked" parts suffering from poor appearance (a "burnt"
color) and/or a deterioration of strength properties. It is
desirable to have a short molding cycle (so as to improve the
productivity of the expensive rotomolding machinery) and a broad
processing window. Thus, the rotomolding composition ideally
provides "properly cooked" parts in a short period of time but does
not become "overcooked" for an extended period of time.
[0007] Therefore, the length of time the resin-filled mold spends
in the oven is critical, because if left too long the polymer will
yellow and/or degrade, thereby negatively affecting the mechanical
and/or physical properties of the molded article (e.g., reducing
impact strength). If the time the resin filled mold spends in the
oven is too short, the sintering and laydown of the molten polymer
will be incomplete, thereby negatively affecting the final physical
and/or mechanical properties of the molded article. Thus, there is
only a narrow temperature and/or time range for achieving the
desired mechanical and/or physical properties of the molded article
(i.e., processing window). Accordingly, it would be advantageous to
widen/broaden this processing window so that parts that have been
processed with longer oven cycle times will still exhibit optimal
mechanical and/or physical properties.
[0008] Various additives are known and have been used in the
rotomolding process to stabilize the polyolefin material and
effectively reduce the production of microstructural defects during
the heating cycle of the rotomolding process, which negatively
affect the molded article. Some of these additives are also known
to affect the cycle time of the rotomolding process. See, e.g.,
Botkin et al., 2004 "An additive approach to cycle time reduction
in rotational molding," Society of Plastics Engineers Rotomolding
Conference, Session 2. For example, the use of stabilizer
combinations of phosphites or phosphonites with sterically hindered
phenols in polyolefins is generally known. Such phenolic/phosphite
or phosphonite blends (e.g., CYANOX.RTM. 2777 antioxidant
(available from Cytec Industries Inc., Woodland Park N.J.)) will
stabilize the resin in the oven for a longer time (resulting in a
broader process window), but requires a longer time in the oven to
achieve maximum physical properties (resulting in a longer cycle
time). Other stabilizer compositions (e.g., hydroxylamine
derivatives blended with phosphites and/or phosphonites and HALS),
allow for faster polymerization and cure times of the resins, but
the processing window remains very narrow. For example,
improvements to widen the processing window by using sterically
hindered amines are disclosed in US Patent Application Publication
No. 2009/0085252.
[0009] Accordingly, the rotational molding of polyolefin resins
requires further improvements in cycle time reduction. A stabilizer
composition that effectively reduces the time for sintering and
laydown of the polymer melt (with reduced oven cycle time), while
maintaining a broad processing window, would be a useful advance in
the field, and would find rapid acceptance in the rotational
molding industry. Shorter cycle times would lead to greater
production yield, higher production efficiency, and, thus, lower
energy uses. Formulations exhibiting a broadened process window
would be easier to fabricate, without concerns about overcuring and
the potential for deterioration of the mechanical properties of the
resulting part. Further, formulations exhibiting both a broadened
process window and shorter cycle time would enable molders to
fabricate parts of different thickness at the same time, thereby
further enhancing productivity.
SUMMARY
[0010] The discovery described in detail hereinbelow include
stabilizer compositions and processes for using same for reducing
cycle time without compromising the processing window in rotational
molding processes related to polyolefin articles. These stabilizer
compositions and processes effectively reduce the time in the oven
needed to reach optimal physical and/or mechanical properties,
thereby reducing cycle times of the rotomolding process and
consequently increasing production yield and production efficiency,
and lowering energy requirements.
[0011] Accordingly, in one aspect of the disclosure, a stabilizer
composition for use in producing a polymeric hollow article in a
rotomolding process, comprises stabilizing amounts of:
[0012] (i) at least one chroman-based compound according to Formula
(V):
##STR00002##
wherein
[0013] R.sub.21 is present at from 1 to 4 positions of the aromatic
portion of Formula (V) and in each instance is independently chosen
from: [0014] C.sub.1-C.sub.12 hydrocarbyl; [0015] NR'R'', wherein
each of R' and R'' is independently chosen from H or
C.sub.1-C.sub.12 hydrocarbyl; or [0016] OR.sub.27, wherein R.sub.27
is chosen from C.sub.1-C.sub.12 hydrocarbyl, COR''' or
Si(R.sub.28).sub.3, wherein R''' is chosen from H or
C.sub.1-C.sub.20 hydrocarbyl and R.sub.28 is chosen from
C.sub.1-C.sub.12 hydrocarbyl or alkoxy; and wherein at least one
instance of R.sub.21 is OR.sub.27;
[0017] R.sub.22 is chosen from H or C.sub.1-C.sub.12
hydrocarbyl;
[0018] R.sub.23 is chosen from H or C.sub.1-C.sub.20
hydrocarbyl;
[0019] each of R.sub.24-R.sub.25 is independently chosen from H,
C.sub.1-C.sub.12 hydrocarbyl or OR'''', wherein R'''' is chosen
from H or C.sub.1-C.sub.12 hydrocarbyl; and
[0020] R.sub.26 is H or a bond which together with R.sub.25 forms
.dbd.O; [0021] (ii) at least one phosphite or phosphonite; and
[0022] (iii) a basic co-additive selected from alkali metal or
alkaline metal salts of higher fatty acids;
[0023] In another aspect of the disclosure, a polymeric hollow
article is made by a process comprising: a) filling a mold with a
polyolefin and a stabilizing amount of the stabilizer composition;
b) rotating the mold around at least one axis while heating the
mold in an oven, thereby fusing the composition and spreading it to
the walls of the mold; c) cooling the mold; and d) opening the mold
to remove the resulting product, thereby producing the polymeric
hollow article.
[0024] In another aspect of the disclosure, the polyolefin, vitamin
E acetate, phosphite or phosphonite compound, and at least one
basic co-additive, and amounts of the vitamin E acetate, phosphite
or phosphonite compound, and at least one basic co-additive are
selected so that at least one of the following results are obtained
in a rotational molding operation employed to produce the polymeric
hollow article, even in the absence of sterically hindered amine
light stabilizers (HALS): a maximum mean failure energy (MFE) of
the polymeric article is reached at a shorter time interval; a
higher MFE of the polymeric article is retained over a longer
heating time; or a processing window is enlarged to a peak internal
air temperature (PIAT) of up to 452.degree. F. with yellowness
index of the article remaining substantially unchanged up to a PIAT
of 452.degree. F.
[0025] These and other objects, features and advantages will become
apparent from the following detailed description taken in
conjunction with the accompanying Figures and Examples.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] FIG. 1 illustrates the mean failure energy (MFE) of
rotomolded parts made with control stabilizer system
(.diamond-solid.) vs. low phenolic stabilizer system
(.tangle-solidup.) vs. a processing stabilizer system according to
the invention (.box-solid.). As seen, the rotomolded part that was
formulated with the stabilizer system according to the invention
(.box-solid.) achieves the highest MFE (as determined by the Dart
Drop Low Temperature Impact Resistance Test Procedure) at a shorter
rotational molding time interval (given by peak internal air
temperature) compared to the rotomolded part that was formulated
with either the control stabilizer system (.diamond-solid.) or the
low phenolic stabilizer system (.tangle-solidup.). Furthermore, the
rotomolded part formulated according to the invention unexpectedly
retains a higher MFE at longer oven times than do the rotomolded
parts formulated with either the control or low phenolic stabilizer
systems. Accordingly, the benefit of using a processing stabilizer
according to the invention in a rotational molding process is due
to the use of a chroman-based compound and not due to use of a
lower amount of phenolic/phosphite.
[0027] FIGS. 2A-B illustrate the MFE of 1/4'' rotomolded parts made
with control stabilizer (.diamond-solid.) and stabilizer system
according to the invention (.box-solid.) in a LLDPE resin provided
by a particular supplier (Resin 1), and the Yellowness Index of the
same rotomolded parts as a function of peak internal air
temperature.
[0028] FIGS. 3A-B illustrate the MFE of 1/4'' rotomolded parts made
with control/state-of-the-art stabilizer (.diamond-solid.);
stabilizer system according to the invention (.box-solid.); and a
second control/state-of-the-art stabilizer (.tangle-solidup.) in a
LLDPE resin provided by a different supplier (Resin 2), and the
Yellowness Index of the same rotomolded parts as a function of peak
internal air temperature.
DETAILED DESCRIPTION
[0029] As summarized above, the compositions and processes using
same that have now been discovered and disclosed herein for the
first time are surprisingly useful for achieving optimal physical
and/or mechanical properties of a rotomolded hollow article in a
shorter period of time in the oven (i.e., cycle time) compared to
those rotomolded articles made with current commercially available
polymer stabilizer packages. Furthermore, the processes and
compositions disclosed herein additionally (and surprisingly)
provide a wider/broader processing window within which the desired
final properties of the rotomolded article can be obtained before
the physical and/or mechanical properties are negatively
affected.
Definitions
[0030] As employed above and throughout the disclosure, the
following terms are provided to assist the reader. Unless otherwise
defined, all terms of art, notations and other scientific
terminology used herein are intended to have the meanings commonly
understood by those of skill in the chemical arts. As used herein
and in the appended claims, the singular forms include plural
referents unless the context clearly dictates otherwise.
[0031] Throughout this specification the terms and substituents
retain their definitions. A comprehensive list of abbreviations
utilized by organic chemists (i.e. persons of ordinary skill in the
art) appears in the first issue of each volume of the Journal of
Organic Chemistry. The list, which is typically presented in a
table entitled "Standard List of Abbreviations" is incorporated
herein by reference.
[0032] The term "hydrocarbyl" is a generic term encompassing
aliphatic, alicyclic and aromatic groups having an all-carbon
backbone and consisting of carbon and hydrogen atoms. In certain
cases, as defined herein, one or more of the carbon atoms making up
the carbon backbone may be replaced or interrupted by a specified
atom or group of atoms, such as by one or more heteroatom of N, O,
and/or S. Examples of hydrocarbyl groups include alkyl, cycloalkyl,
cycloalkenyl, carbocyclic aryl, alkenyl, alkynyl, alkylcycloalkyl,
cycloalkylalkyl, cycloalkenylalkyl, and carbocyclic aralkyl,
alkaryl, aralkenyl and aralkynyl groups. Such hydrocarbyl groups
can also be optionally substituted by one or more substituents as
defined herein. Accordingly, the chemical groups or moieties
discussed in the specification and claims should be understood to
include the substituted or unsubstituted forms. The examples and
preferences expressed below also apply to each of the hydrocarbyl
substituent groups or hydrocarbyl-containing substituent groups
referred to in the various definitions of substituents for
compounds of the formulas described herein unless the context
indicates otherwise.
[0033] Preferred non-aromatic hydrocarbyl groups are saturated
groups such as alkyl and cycloalkyl groups. Generally, and by way
of example, the hydrocarbyl groups can have up to fifty carbon
atoms, unless the context requires otherwise. Hydrocarbyl groups
with from 1 to 30 carbon atoms are preferred. Within the sub-set of
hydrocarbyl groups having 1 to 30 carbon atoms, particular examples
are C.sub.1-20 hydrocarbyl groups, such as C.sub.1-12 hydrocarbyl
groups (e.g. C.sub.1-6 hydrocarbyl groups or C.sub.1-4 hydrocarbyl
groups), specific examples being any individual value or
combination of values selected from C.sub.1 through C.sub.30
hydrocarbyl groups.
[0034] Alkyl is intended to include linear, branched, or cyclic
hydrocarbon structures and combinations thereof. Lower alkyl refers
to alkyl groups of from 1 to 6 carbon atoms. Examples of lower
alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, s-
and t-butyl and the like. Preferred alkyl groups are those of
C.sub.30 or below.
[0035] Alkoxy or alkoxyalkyl refers to groups of from 1 to 20
carbon atoms of a straight, branched, cyclic configuration and
combinations thereof attached to the parent structure through an
oxygen. Examples include methoxy, ethoxy, propoxy, isopropoxy,
cyclopropyloxy, cyclohexyloxy and the like.
[0036] Acyl refers to formyl and to groups of 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11 and 12 carbon atoms of a straight, branched, cyclic
configuration, saturated, unsaturated and aromatic and combinations
thereof, attached to the parent structure through a carbonyl
functionality. Examples include acetyl, benzoyl, propionyl,
isobutyryl, t-butoxycarbonyl, benzyloxycarbonyl and the like.
Lower-acyl refers to groups containing one to six carbons.
[0037] References to "carbocyclic" or "cycloalkyl" groups as used
herein shall, unless the context indicates otherwise, include both
aromatic and non-aromatic ring systems. Thus, for example, the term
includes within its scope aromatic, non-aromatic, unsaturated,
partially saturated and fully saturated carbocyclic ring systems.
In general, such groups may be monocyclic or bicyclic and may
contain, for example, 3 to 12 ring members, more usually 5 to 10
ring members. Examples of monocyclic groups are groups containing
3, 4, 5, 6, 7, and 8 ring members, more usually 3 to 7, and
preferably 5 or 6 ring members. Examples of bicyclic groups are
those containing 8, 9, 10, 11 and 12 ring members, and more usually
9 or 10 ring members. Examples of non-aromatic
carbocycle/cycloalkyl groups include c-propyl, c-butyl, c-pentyl,
c-hexyl, and the like. Examples of C.sub.7 to C.sub.10 polycyclic
hydrocarbons include ring systems such as norbornyl and
adamantyl.
[0038] Aryl (carbocyclic aryl) refers to a 5- or 6-membered
aromatic carbocycle ring containing; a bicyclic 9- or 10-membered
aromatic ring system; or a tricyclic 13- or 14-membered aromatic
ring system. The aromatic 6- to 14-membered carbocyclic rings
include, e.g., substituted or unsubstituted phenyl groups, benzene,
naphthalene, indane, tetralin, and fluorene.
[0039] Substituted hydrocarbyl, alkyl, aryl, cycloalkyl, alkoxy,
etc. refer to the specific substituent wherein up to three H atoms
in each residue are replaced with alkyl, halogen, haloalkyl,
hydroxy, alkoxy, carboxy, carboalkoxy (also referred to as
alkoxycarbonyl), carboxamido (also referred to as
alkylaminocarbonyl), cyano, carbonyl, nitro, amino, alkylamino,
dialkylamino, mercapto, alkylthio, sulfoxide, sulfone, acylamino,
amidino, phenyl, benzyl, halobenzyl, heteroaryl, phenoxy,
benzyloxy, heteroaryloxy, benzoyl, halobenzoyl, or
loweralkylhydroxy.
[0040] The term "halogen" means fluorine, chlorine, bromine or
iodine.
[0041] As used herein, the term "chroman-based compound" refers to
those compounds having a functional chroman group as part of the
compound. In certain embodiments the chroman-based compound will be
substituted. In other embodiments, the chroman-based compound can
include chromanones. Coumarin and tocotrienols are specific
examples of chroman-based compounds.
[0042] The terms "cycle time" or "molding cycle" as used herein are
given their ordinary meaning as commonly understood by those of
skill in the rotomolding arts and refer to the time from one point
in the cycle to the corresponding point in the next repeated
sequence (i.e., the time required to produce a plastic part in a
molding operation as measured from a point of one operation to the
same point of the first repeat of the operation).
[0043] The terms "optimal mechanical property" or "optimal physical
property" as used herein refer to rotomolded parts having the most
desirable: impact strength, coalescence or scintering of polymer
particles, and general appearance such as color.
[0044] All numbers expressing quantities of ingredients, reaction
conditions, and so forth used in the specification and claims are
to be understood as being modified in all instances by the term
"about." Accordingly, unless indicated to the contrary, the
numerical parameters set forth in the specification and attached
claims are approximations that may vary depending upon the desired
properties sought to be obtained by the present invention. At the
very least, and not as an attempt to limit the application of the
doctrine of equivalents to the scope of the claims, each numerical
parameter should be construed in light of the number of significant
digits and ordinary rounding approaches.
Processes
[0045] Rotational molding technology is well known and described in
the literature. Many aspects of the rotational molding process are
described, for example, by R. J. Crawford and J. L. Throne in
Rotational Molding Technology, Plastics Design Library, William
Andrew Publishing, 2001. The rotomolded articles described herein
are made from stabilized polymer compositions according to the
invention using rotational molding techniques generally accepted by
those skilled in the art as being representative of commercial
rotational molding processes. In general, these rotational molding
techniques involve the use of a rotational mold and an oven. A
polymer composition (e.g., a stabilized polymer composition
including a stabilizer composition and a polymer composition as
described herein) is placed in a mold possessing a predetermined
shape. The mold is heated within the oven at a predetermined rate
to a peak temperature. During heating, the resin melts and the mold
is rotated in two or three dimensions to ensure that the melted
resin evenly coats the interior surfaces of the mold. Optionally,
the melted resin may be cured for a predetermined time. After
heating is complete, the mold is removed from the oven and cooled
(with the mold optionally being in rotation). Once cool, the formed
plastic part is removed from the mold.
[0046] Surprisingly, it has now been found that when at least one
chroman-based compound is added to the rotomolding resin
formulation the time at which it takes to reach peak internal air
temperature (PIAT) is reduced and a significantly broader
processing window towards higher temperatures is achieved without
adversely affecting the physical and/or mechanical properties of
the molded article.
[0047] Consequently, in one aspect the invention provides a process
for reducing cycle time while maintaining an enlarged process
window in a rotational molding process for producing a polymeric
hollow article by subjecting a polymer composition and a
polymer-stabilizing amount of a stabilizer composition to a
rotational molding process, wherein the stabilizer composition
includes at least one chroman-based compound according to Formula V
as described herein.
[0048] In certain embodiments, the cycle time of the process will
be reduced by at least 4%, at least 5%, at least 10%, at least 15%,
or at least 20%, at least 25%, at least 40%, or at least 50% as
compared to a process that does not include at least one
chroman-based compound in the resin formulation.
[0049] In another aspect, the invention provides a process for
producing a polymeric hollow article by a) filling a mold with a
polymer composition and a polymer-stabilizing amount of a
stabilizer composition, wherein the stabilizer composition includes
at least one chroman-based compound according to Formula V as
described herein; b) rotating the mold around at least one axis
while heating the mold in an oven, thereby fusing the composition
and spreading it to the walls of the mold; c) cooling the mold; and
d) opening the mold to remove the resulting product, thereby
producing a polymeric hollow article.
[0050] During the rotomolding process, the temperature of the oven
can reach from 70.degree. C. to 400.degree. C., preferably from
280.degree. C. to 400.degree. C., and more preferably from
310.degree. C. to 400.degree. C.
[0051] The stabilized polymer compositions suitable for use with
the aforementioned processes are further described below.
Stabilizer Compositions
[0052] A stabilizer composition for use in producing a polymeric
hollow article in a rotomolding process, comprises a stabilizing
amount of:
[0053] (i) at least one chroman-based compound according to Formula
(V):
##STR00003##
wherein
[0054] R.sub.21 is present at from 1 to 4 positions of the aromatic
portion of Formula (V) and in each instance is independently chosen
from: [0055] C.sub.1-C.sub.12 hydrocarbyl; [0056] NR'R'', wherein
each of R' and R'' is independently chosen from H or
C.sub.1-C.sub.12 hydrocarbyl; or [0057] OR.sub.27, wherein R.sub.27
is chosen from C.sub.1-C.sub.12 hydrocarbyl, COR''', or
Si(R.sub.28).sub.3, wherein R''' is chosen from H or
C.sub.1-C.sub.20 hydrocarbyl and R.sub.28 is chosen from
C.sub.1-C.sub.12 hydrocarbyl or alkoxy; and wherein at least one
instance of R.sub.21 is OR.sub.27;
[0058] R.sub.22 is chosen from H or C.sub.1-C.sub.12
hydrocarbyl;
[0059] R.sub.23 is chosen from H or C.sub.1-C.sub.20
hydrocarbyl;
[0060] each of R.sub.24-R.sub.25 is independently chosen from H,
C.sub.1-C.sub.12 hydrocarbyl or OR'''', wherein R'''' is chosen
from H or C.sub.1-C.sub.12 hydrocarbyl; and
[0061] R.sub.26 is H or a bond which together with R.sub.25 forms
.dbd.O;
[0062] (ii) at least one phosphite or phosphonite; and
[0063] (iii) a basic co-additive selected from alkali metal or
alkaline metal salts of higher fatty acids.
[0064] The stabilizer compositions according to the invention and
suitable for use with the polymer compositions for the rotomolding
processes as described herein include at least one chroman-based
compound according to Formula (V):
##STR00004##
wherein
[0065] R.sub.21 is present at from 0 to 4 positions of the aromatic
portion of Formula (V) and in each instance is independently chosen
from: [0066] C.sub.1-C.sub.12 hydrocarbyl; [0067] NR'R'', wherein
each of R' and R'' is independently chosen from H or
C.sub.1-C.sub.12 hydrocarbyl; or [0068] OR.sub.27, wherein R.sub.27
is chosen from C.sub.1-C.sub.12 hydrocarbyl, COR''' or
Si(R.sub.28).sub.3, wherein R''' is chosen from H or
C.sub.1-C.sub.20 hydrocarbyl; and wherein R.sub.28 is chosen from
C.sub.1-C.sub.12 hydrocarbyl or alkoxy;
[0069] R.sub.22 is chosen from H or C.sub.1-C.sub.12
hydrocarbyl;
[0070] R.sub.23 is chosen from H or C.sub.1-C.sub.20 hydrocarbyl;
and
[0071] each of R.sub.24-R.sub.25 is independently chosen from H,
C.sub.1-C.sub.12 hydrocarbyl or OR'''', wherein R'''' is chosen
from H or C.sub.1-C.sub.12 hydrocarbyl; and
[0072] R.sub.26 is H or a bond which together with R.sub.25 forms
.dbd.O.
[0073] In certain embodiments, R.sub.21 is present as acyl and
methyl.
[0074] In certain embodiments, R.sub.23 is a C.sub.1-C.sub.18
hydrocarbyl.
[0075] In some embodiments, the chroman-based compound according to
Formula (V) is a tocotrienol, including, but not limited to,
.alpha.-tocotrienol; .beta.-tocotrienol; .gamma.-tocotrienol, and
6-tocotrienol. In other embodiments, the chroman-based compound is
a tocopherol including, but not limited to, .alpha.-tocopherol,
0-tocopherol, .gamma.-tocopherol, and 6-tocopherol.
[0076] In some embodiments, the chroman-based compound is vitamin E
acetate according to Formula (Va):
##STR00005##
wherein R.sub.21 is --OC(O)CH.sub.3.
[0077] In certain embodiments, the stabilizer composition includes
two or more chroman-based compounds according to Formula (V).
[0078] The chroman-based compound is present from 0.001% to 5.0% by
weight of the total weight of a stabilized polymer composition,
preferably from 0.01% to 2.0% by weight of the total weight of the
stabilized polymer composition, and more preferably from 0.01% to
1.0% by weight of the total weight of the stabilized polymer
composition. In certain embodiments, the chroman-based compound is
present at about 0.05% by weight of the total weight of the
stabilized polymer composition. In some embodiments the polymer is
a polyolefin and the stabilized polymer composition is a
polyolefin.
[0079] In certain embodiments, the stabilizer composition can
further include at least one compound chosen from the group of
organic phosphites or phosphonites. In some embodiments the organic
phosphite or phosphonite compound includes at least one organic
phosphite or phosphonite chosen from:
[0080] (i) a compound according to Formulas (1)-(7):
##STR00006##
in which the indices are integral and
[0081] n is 2, 3 or 4; p is 1 or 2; q is 2 or 3; y is 1, 2 or 3;
and z is 1 to 6; A.sub.1, if n is 2, is C.sub.2-C.sub.18 alkylene;
C.sub.2-C.sub.12 alkylene interrupted by oxygen, sulfur or
--NR.sub.4--; a radical of the formula
##STR00007##
or phenylene;
[0082] A.sub.1, if n or q is 3, is a trivalent radical of the
formula --C.sub.rH.sub.2r-1--; wherein r is an integer from 4 to
12;
[0083] A.sub.1, if n is 4, is
##STR00008##
[0084] B is a direct bond, --CH.sub.2--, --CHR.sub.4--,
--CR.sub.1R.sub.4--, sulfur, C.sub.5-C.sub.7 cycloalkylidene, or
cyclohexylidene which is substituted by from 1 to 4 C.sub.1-C.sub.4
alkyl radicals in position 3, 4 and/or 5;
[0085] D.sub.1, if p is 1, is C.sub.1-C.sub.4 alkyl and, if p is 2,
is --CH.sub.2OCH.sub.2--;
[0086] D.sub.2 is C.sub.1-C.sub.4 alkyl;
[0087] E, if y is 1, is C.sub.1-C.sub.18 alkyl, --OR.sub.1 or
halogen;
[0088] E, if y is 2, is --O-A.sub.2-O--, wherein A.sub.2 is as
defined for A.sub.1 when n is 2;
[0089] E, if y is 3, is a radical of the formula
R.sub.4C(CH.sub.2O--).sub.3 or N(CH.sub.2CH.sub.2O--).sub.3;
[0090] Q is the radical of an at least z-valent mono- or
poly-alcohol or phenol, this radical being attached via the oxygen
atom of the OH group of the mono- or poly-alcohol or phenol to the
phosphorus atom;
[0091] R.sub.1, R.sub.2 and R.sub.3 independently of one another
are C.sub.1-C.sub.18 alkyl which is unsubstituted or substituted by
halogen, --COOR.sub.4, --CN or --CONR.sub.4R.sub.4;
C.sub.2-C.sub.18 alkyl interrupted by oxygen, sulfur or
--NR.sub.4--; C.sub.7-C.sub.9 phenylalkyl; C.sub.5-C.sub.12
cycloalkyl, phenyl or naphthyl; naphthyl or phenyl substituted by
halogen, 1 to 3 alkyl radicals or alkoxy radicals having a total of
1 to 18 carbon atoms or by C.sub.7-C.sub.9 phenylalkyl; or a
radical of the formula
##STR00009##
in which m is an integer from the range 3 to 6;
[0092] R.sub.4 is hydrogen, C.sub.1-C.sub.5 alkyl, C.sub.5-C.sub.12
cycloalkyl or C.sub.7-C.sub.9 phenylalkyl;
[0093] R.sub.5 and R.sub.6 independently of one another are
hydrogen, C.sub.1-C.sub.5 alkyl or C.sub.5-C.sub.6 cycloalkyl;
[0094] R.sub.7 and R.sub.8, if q is 2, independently of one another
are C.sub.1-C.sub.4 alkyl or together are a
2,3-dehydropentamethylene radical; and
[0095] R.sub.7 and R.sub.8, if q is 3, are methyl;
[0096] each instance of R.sub.14 is independently hydrogen,
C.sub.1-C.sub.9 alkyl or cyclohexyl;
[0097] each instance of R.sub.15 is independently hydrogen or
methyl;
[0098] X and Y are each a direct bond or oxygen;
[0099] Z is a direct bond, methylene, --C(R.sub.16).sub.2-- or
sulfur; and
[0100] R.sub.16 is C.sub.1-C.sub.8 alkyl;
[0101] (ii) a trisarylphosphite according to Formula (8):
##STR00010##
wherein R.sub.17 is present at from 0 to 5 positions of the
aromatic portion of Formula (8) and in each instance is
independently chosen from C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20
cycloalkyl, C.sub.4-C.sub.20 alkyl cycloalkyl, C.sub.6-C.sub.10
aryl or C.sub.7-C.sub.20 alkylaryl; or
[0102] (iii) mixtures of (i) and (ii).
[0103] In some embodiments, the following organic phosphites or
phosphonites are preferred: triphenyl phosphite; diphenyl alkyl
phosphites; phenyl dialkyl phosphites; trilauryl phosphite;
trioctadecyl phosphite; distearyl pentaerythritol phosphite;
tris(2,4-di-t-butylphenyl) phosphite; tris(nonylphenyl) phosphite;
a compound of formulae (A), (B), (C), (D), (E), (F), (G), (H), (J),
(K) or (L):
##STR00011## ##STR00012##
2-butyl-2-ethyl-1,3-propanediol 2,4,6-tri-t-butylphenol phosphite;
bis-(2,6-di-t-butyl-4-methlphenyl) pentaerythritol diphosphite;
2-butyl-2-ethyl-1,3-propanediol 2,4-di-cumylphenol phosphite;
2-butyl-2-ethyl-1,3-propanediol 4-methyl-2,6-di-t-butylphenol
phosphite or bis-(2,4,6-tri-t-butyl-phenyl) pentaerythritol
diphosphite.
[0104] The following organic phosphites and phosphonites are
particularly suitable for use in the rotomolding processes
described herein: tris(2,4-di-t-butylphenyl)phosphite
(IRGAFOS.RTM.168); bis(2,4-dicumylphenyl)pentaerythritol
diphosphite (DOVERPHOS.RTM. S9228); and
tetrakis(2,4-di-t-butylphenyl)4,4'-biphenylene-diphosphonite
(IRGAFOS.RTM. P-EPQ).
[0105] The organic phosphites or phosphonites can be present in an
amount from 0.01% to 10% by weight based on the weight of the
polymer material to be stabilized. Preferably, the amount of
organic phosphite or phosphonite is available from 0.05% to 5%, and
more preferably from 0.1% to 3% by weight based on the weight of
the polymer material to be stabilized.
[0106] In certain embodiments, the stabilizer composition can
further include at least one hindered phenol compound. Suitable
hindered phenols for use with the rotomolding processes described
herein include, but are not limited to, those having a molecular
fragment according to one or more of Formula (IVa), (IVb), or
(IVc):
##STR00013##
wherein "" indicates the point of attachment (via a carbon bond) of
the molecular fragment to a parent compound, and wherein R.sub.18
of Formula (IVa), (IVb), and (IVc) is independently chosen from
hydrogen or a C.sub.1-4 hydrocarbyl; R.sub.19 and R.sub.20 of
Formula (IVa), (IVb), and (IVc) are the same or different and are
independently chosen from hydrogen or a C.sub.1-C.sub.20
hydrocarbyl; and R.sub.37 of Formula (IVa), (IVb), and (IVc) is
independently chosen from a C.sub.1-C.sub.12 hydrocarbyl. In some
embodiments, R.sub.18 and R.sub.37 are independently chosen from
methyl or t-butyl.
[0107] The following compounds exemplify some hindered phenols that
are suitable for use in the compositions and processes disclosed
herein:
(1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6--
(1H,3H,5H)-trione;
1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-
-trione (IRGANOX.RTM. 3114);
1,1,3-tris(2'-methyl-4'-hydroxy-5'-t-butylphenyl)butane;
triethylene glycol
bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate];
4,4'-thiobis(2-t-butyl-5-methylphenol); 2,2'-thiodiethylene
bis[3-(3-t-butyl-4-hydroxyl-5-methylphenyl)propionate]; octadecyl
3-(3'-t-butyl-4'-hydroxy-5'-methylphenyl)propionate;
tetrakismethylene(3-t-butyl-4-hydroxy-5-methylhydrocinnamate)methane;
N,N'-hexamethylene
bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionamide];
di(4-t-butyl-3-hydroxy-2,6-dimethyl benzyl) thiodipropionate;
octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate; or mixtures
thereof.
[0108] Other phenols also suitable for use with processes and
compositions of the invention are known to those of skill in the
art and include, for example:
[0109] 2,6-di-tert-butyl-4-methylphenol;
2-tert-butyl-4,6-dimethylphenol; 2,6-di-tert-butyl-4-ethylphenol;
2,6-di-tert-butyl-4-n-butylphenol; 2,6-di-tert-butyl-4
isobutylphenol; 2,6-dicyclopentyl-4-methylphenol;
2-(.alpha.-methylcyclohexyl)-4,6 dimethylphenol;
2,6-di-octadecyl-4-methylphenol; 2,4,6,-tricyclohexyphenol; and
2,6-di-tert-butyl-4-methoxymethylphenol;
[0110] 2,2'-methylene-bis-(6-tert-butyl-4-methylphenol)
(CYANOX.RTM. 2246); 2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol)
(CYANOX.RTM. 425);
2,2'-methylene-bis-(4-methyl-6-(.alpha.-methylcyclohexyl)phenol);
2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol);
2,2'-methylene-bis-(6-nonyl-4-methylphenol);
2,2'-methylene-bis-(6-nonyl-4methylphenol);
2,2'-methylene-bis-(6-(.alpha.-methylbenzyl)-4-nonylphenol);
2,2'-methylene-bis-(6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonyl-phenol);
2,2'-methylene-bis-(4,6-di-tert-butylphenol);
2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol);
4,4'methylene-bis-(2,6-di-tert-butylphenol);
4,4'-methylene-bis-(6-tert-butyl-2-methylphenol);
1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenol)butane
2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol;
1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)butane;
1,1-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-3-dodecyl-mercaptobutane;
ethyleneglycol-bis-(3,3,-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate)-d-
i-(3-tert-butyl-4-hydroxy-5-methylpenyl)-dicyclopentadiene;
di-(2-(3'-tert-butyl-2'hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphen-
y-1)terephthalate; and other phenolics such as monoacrylate esters
of bisphenols such as ethylidiene bis-2,4-di-t-butylphenol
monoacrylate ester;
[0111] Hydroquinones, such as 2,6-di-tert-butyl-4-methoxyphenol;
2,5-di-tert-butyihydroquinone; 2,5-di-tert-amyl-hydroquinone; and
2,6-diphenyl-4-octadecyloxyphenol; and
[0112] Thiodiphenyl ethers such as
2,2'-thio-bis-(6-tert-butyl-4-methylphenol);
2,2'-thio-bis-(4-octylphenol);
4,4'-thio-bis-(6-tert-butyl-3-methylphenol); and
4,4'-thio-bis-(6-tert-butyl-2-methylphenol).
[0113] A stabilizer composition including at least one
chroman-based compound according to Formula V is suitable for
stabilizing polyolefin hollow articles which are prepared by the
rotomolding process. Examples of polyolefins suitable for such use
with the stabilizer composition according to the invention include
at least the following:
[0114] (A) Polymers of monoolefins and diolefins, for example
polypropylene, polyisobutylene, polybut-1-ene,
poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as
polymers of cycloolefins, for instance of cyclopentene or
norbornene, polyethylene (which optionally can be crosslinked), for
example high density polyethylene (HDPE), high density and high
molecular weight polyethylene (HDPE-HMW), high density and
ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density
polyethylene (MDPE), low density polyethylene (LDPE), linear low
density polyethylene (LLDPE), (VLDPE) and (ULDPE);
[0115] (B) Polyolefins, i.e. the polymers of monoolefins
exemplified in (A), preferably polyethylene and polypropylene, can
be prepared by different, and especially by the following,
methods:
[0116] i) radical polymerisation (normally under high pressure and
at elevated temperature); or
[0117] ii) catalytic polymerisation using a catalyst that normally
contains one or more than one metal of groups IVb, Vb, VIb or VIII
of the Periodic Table. These metals usually have one or more than
one ligand, typically oxides, halides, alcoholates, esters, ethers,
amines, alkyls, alkenyls and/or aryls that may be either p- or
s-coordinated. These metal complexes may be in the free form or
fixed on substrates, typically on activated magnesium chloride,
titanium(III) chloride, alumina or silicon oxide. These catalysts
may be soluble or insoluble in the polymerisation medium. The
catalysts can be used by themselves in the polymerisation or
further activators may be used, typically metal alkyls, metal
hydrides, metal alkyl halides, metal alkyl oxides or metal
alkyloxanes, said metals being elements of groups Ia, IIa and/or
IIIa of the Periodic Table. The activators may be modified
conveniently with further ester, ether, amine or silyl ether
groups. These catalyst systems are usually termed Phillips,
Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or
single site catalysts (SSC).
[0118] (C) Mixtures of the polymers mentioned under (A), for
example mixtures of polypropylene with polyisobutylene,
polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and
mixtures of different types of polyethylene (for example
LDPE/HDPE).
[0119] (D) Copolymers of monoolefins and diolefins with each other
or with other vinyl monomers, for example ethylene/propylene
copolymers, linear low density polyethylene (LLDPE) and mixtures
thereof with low density polyethylene (LDPE), propylene/but-1-ene
copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene
copolymers, ethylene/hexene copolymers, ethylene/methylpentene
copolymers, ethylene/heptene copolymers, ethylene/octene
copolymers, propylene/butadiene copolymers, isobutylene/isoprene
copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl
methacrylate copolymers, ethylene/vinyl acetate copolymers and
their copolymers with carbon monoxide or ethylene/acrylic acid
copolymers and their salts (ionomers) as well as terpolymers of
ethylene with propylene and a diene such as hexadiene,
dicyclopentadiene or ethylidene-norbornene; and mixtures of such
copolymers with one another and with polymers mentioned in (A)
above, for example polypropylene/ethylene-propylene copolymers,
LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic
acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or
random polyalkylene/carbon monoxide copolymers and mixtures thereof
with other polymers, for example polyamides.
[0120] In some embodiments, the polyolefin is chosen from:
[0121] (i) polymers of monoolefins chosen from polypropylene,
polyisobutylene, polybut-1-ene, or poly-4-methylpent-1-ene;
[0122] (ii) polymers of diolefins chosen from polyisoprene or
polybutadiene;
[0123] (iii) polymers of cycloolefins chosen from cyclopentene or
norbornene;
[0124] (iv) polyethylene chosen from optionally crosslinked
polyethylene, high density polyethylene (HDPE), high density and
high molecular weight polyethylene (HDPE-HMW), high density and
ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density
polyethylene (MDPE), low density polyethylene (LDPE), linear low
density polyethylene (LLDPE), very low density polyethylene
(VLDPE), or ultralow density polyethylene (ULDPE);
[0125] (v) copolymers of the monoolefins, diolefins, or
cycloolefins of any of (i) to (iv); or
[0126] vi) mixtures of any of (i) to (v).
[0127] In some embodiments, the polyolefin is at least one of
linear low density polyethylene (LLDPE), medium density
polyethylene (MDPE), high density polyethylene (HDPE), or
polypropylene.
[0128] The stabilized polymer compositions according to the
invention may further include one or more co-stabilizers and/or
additives that include, but are not limited to, hindered amine
light stabilizers, hindered hydroxyl benzoates, nickel phenolates,
ultraviolet light stabilizers, or mixtures thereof in an amount
effective to stabilize the polymer composition against the
degradative effects of visible and/or ultraviolet light
radiation.
[0129] Suitable hindered amine light stabilizers for use with the
processes and stabilized polymer compositions according to the
invention include, for example, compounds having a molecular
fragment according to Formula (VI):
##STR00014##
wherein R.sub.31 is chosen from hydrogen, OH, C.sub.1-C.sub.20
hydrocarbyl, --CH.sub.2CN, C.sub.1-C.sub.12 acyl or
C.sub.1-C.sub.18 alkoxy; R.sub.38 is chosen from hydrogen or
C.sub.1-C.sub.8 hydrocarbyl; and each of R.sub.29, R.sub.30,
R.sub.32, and R.sub.33 is independently chosen from
C.sub.1-C.sub.20 hydrocarbyl; or R.sub.29 and R.sub.30 and/or
R.sub.32 and R.sub.33 taken together with the carbon to which they
are attached form a C.sub.5-C.sub.1O cycloalkyl; or Formula
(VIa)
##STR00015##
[0130] wherein [0131] m is an integer from 1 to 2; [0132] R.sub.39
is chosen from hydrogen, OH, C.sub.1-C.sub.20 hydrocarbyl,
--CH.sub.2CN, C.sub.1-C.sub.12 acyl or C.sub.1-C.sub.18 alkoxy;
and
[0133] each of G.sub.1-G.sub.4 is independently a C.sub.1-C.sub.20
hydrocarbyl.
[0134] Hindered amine light stabilizers particularly suitable for
use with the present invention include, but are not limited to,
bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate;
bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl
3,5-di-tert-butyl-4-hydroxybenzylmalonate; a condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid; 2,2,6,6-tetramethylpiperidin-4-yl stearate;
2,2,6,6-tetramethylpiperidin-4-yl dodecanate;
1,2,2,6,6-pentamethylpiperidin-4-yl stearate;
1,2,2,6,6-pentamethylpiperidin-4-yl dodecanate; a condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine;
tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate;
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylat-
e; 4-benzoyl-2,2,6,6-tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-bu-
tylbenzyl)malonate;
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate; a condensate
of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine
and 4-morpholino-2,6-dichloro-1,3,5-triazine; a condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane; a condensate of
2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis-(3-aminopropylamino)ethane;
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d-
ione;
3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;
3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5--
dione;
3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-di-
one; a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine; a condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; a condensate of
1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine
and 4-butylamino-2,2,6,6-tetramethylpiperidine;
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane;
oxo-piperanzinyl-triazines; or a reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
and epichlorohydrin; N-alkoxy hindered amine light stabilizers
including, but not limited to,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)
butane-1,2,3,4-tetracarboxylate (MARK.RTM. LA-57;);
1,2,3,4-butanetetracarboxylic acid,
tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl)ester (MARK.RTM.
LA-52); 1,2,3,4-butanetetracarboxylic acid,
1,2,2,6,6-pentamethyl-4-piperdinyl tridecyl ester (MARK.RTM.
LA-62); 1,2,3,4-butanetetracarboxylic acid,
2,2,6,6-tetramethyl-4-piperidinyl tridecyl ester (MARK.RTM. LA-67);
1,2,3,4-butanetetracarboxylic acid, polymer with
2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]-undecane-3,9-diethanol,1,-
2,2,6,6-pentamethyl-4-piperdinyl ester (MARK.RTM. LA-63);
1,2,3,4-butanetetracarboxylic acid, polymer with
2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]-undecane-3,9-diethanol,
2,2,6,6-tetramethyl-4-piperdinyl ester (MARK.RTM. LA-68);
bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate
(MARK.RTM. LA-81; aka STAB.RTM. LA-81 available from Adeka
Palmarole, Saint-Louis, France); TINUVIN.RTM. 123; TINUVIN.RTM. NOR
371; TINUVIN.RTM. XT-850/XT-855; FLAMESTAB.RTM. NOR 116; or those
disclosed in EP 0 889 085;
[0135] hydroxyl-substituted N-alkoxy HALS including, but not
limited to, those disclosed in U.S. Pat. No. 6,271,377 such as
1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-piperdinol;
1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperi-
dine;
1-(4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-octadec-
anoyloxy-2-methylpropane;
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperdinol; or a reaction
product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperdinol and
dimethylsuccinate;
[0136] any of the tetramethylpiperidyl groups disclosed in WO
2007/104689 including, but not limited to,
2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one
(HOSTAVIN.RTM. N20); the ester of 2,2,6,6-tetramethyl-4-piperidinol
with higher fatty acids (CYASORB.RTM. 3853);
3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione
(SANDUVOR.RTM. 3055); and their wax reaction products such as HALS
NOW (LS X--N--O--W1); or
[0137] piperazinone compounds and derivatives thereof disclosed in
U.S. Pat. Nos. 6,843,939; 7,109,259; 4,240,961; 4,480,092;
4,629,752; 4,639,479; 5,013,836; 5,310,771; or WO 88/08863.
[0138] The hindered amine light stabilizers include, but are not
limited to, for example, 1H-Pyrrole-2,5-dione, 1-octadecyl-,
polymer with (1-methylethenyl)benzene and
1-(2,2,6,6-tetramethyl-4-piperidinyl)-1H-pyrrole-2,5-dione;
piperazinone,
1,1',1''-[1,3,5-triazine-2,4,6-triyltris[(cyclohexylimino)-2,1-ethanediyl-
]]tris[3,3,5,5-tetramethyl-; piperazinone,
1,1',1''-[1,3,5-triazine-2,4,6-triyltris[(cyclohexylimino)-2,1-ethanediyl-
]]tris[3,3,4,5,5-pentamethyl-; the reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
and epichlorohydrin; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; the condensate of
1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine
and 4-butylamino-2,2,6,6-tetramethylpiperidine; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine; the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane; the condensate of
2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis-(3-aminopropylamino)ethane;
2-[(2-hydroxyethyl)amino]-4,6-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylp-
iperidin-4-yl)butylamino-1,3,5-triazine; propanedioic acid,
[(4-methoxyphenyl)-methylene]-bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)
ester;
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracar-
boxylate; benzenepropanoic acid,
3,5-bis(1,1-dimethylethyl)-4-hydroxy-,
1-[2-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]ethyl]--
2,2,6,6-tetramethyl-4-piperidinyl ester;
N-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N'-dodecyloxalamide;
tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate;
1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid,
bis(1,2,2,6,6-pentamethyl-4-piperidinyl):
1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid,
bis(2,2,6,6-tetramethyl-4-piperidinyl); the condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine;
1,2,3,4-butanetetracarboxylic acid,
1,2,2,6,6-pentamethyl-4-piperidinyl tridecyl ester;
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylat-
e; 1,2,3,4-butanetetracarboxylic acid,
2,2,6,6-tetramethyl-4-piperidinyl tridecyl ester;
tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxyl-
ate; mixture of
2,2,4,4-tetramethyl-21-oxo-7-oxa-3.20-diazaspiro(5.1.11.2)-heneicosane-20-
-propanoic acid-dodecylester and
2,2,4,4-tetramethyl-21-oxo-7-oxa-3.20-diazaspiro(5.1.11.2)-heneicosane-20-
-propanoic acid-tetradecylester;
1H,4H,5H,8H-2,3a,4a,6,7a,8a-hexaazacyclopenta[def]fluorene-4,8-dione,
hexahydro-2,6-bis(2,2,6,6-tetramethyl-4-piperidinyl)-;
polymethyl[propyl-3-oxy(2',2',6',6'-tetramethyl-4,4'-piperidinyl)]siloxan-
e;
polymethyl[propyl-3-oxy(1',2',2',6',6'-pentamethyl-4,4'-piperidinyl)]si-
loxane; copolymer of methylmethacrylate with ethyl acrylate and
2,2,6,6-tetramethylpiperidin-4-yl acrylate; copolymer of mixed
C.sub.20 to C.sub.24 alpha-olefins and
(2,2,6,6-tetramethylpiperidin-4-yl)succinimide;
1,2,3,4-butanetetracarboxylic acid, polymer with
.beta.,.beta.,.beta.',.beta.'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]unde-
cane-3,9-diethanol, 1,2,2,6,6-pentamethyl-4-piperidinyl ester;
1,2,3,4-butanetetracarboxylic acid, polymer with
.beta.,.beta.,.beta.',.beta.'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]unde-
cane-3,9-diethanol, 2,2,6,6-tetramethyl-4-piperidinyl ester
copolymer; 1,3-benzenedicarboxamide,
N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl;
1,1'-(1,10-dioxo-1,10-decanediyl)-bis(hexahydro-2,2,4,4,6-pentamethylpyri-
midine; ethane diamide,
N-(1-acetyl-2,2,6,6-tetramethylpiperidinyl)-N'-dodecyl; formamide,
N,N'-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl);
D-glucitol,
1,3:2,4-bis-O-(2,2,6,6-tetramethyl-4-piperidinylidene)-;
2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane;
propanamide,
2-methyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)-2-[(2,2,6,6-tetramethyl-4--
piperidinyl)amino]-;
7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-20-propanoic acid,
2,2,4,4-tetramethyl-21-oxo-, dodecyl ester;
N-(2,2,6,6-tetramethylpiperidin-4-yl)-.beta.-aminopropionic acid
dodecyl ester;
N-(2,2,6,6-tetramethylpiperidin-4-yl)-N'-aminooxalamide;
propanamide,
N-(2,2,6,6-tetramethyl-4-piperidinyl)-3-[(2,2,6,6-tetramethyl-4-piperidin-
yl)amino]-; mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione;
3-dodecyl-1-(1-ethanoyl-2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-
-dione; bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl
3,5-di-tert-butyl-4-hydroxybenzylmalonate;
tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate;
1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone);
4-benzoyl-2,2,6,6-tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-bu-
tylbenzyl)malonate;
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate;
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d-
ione;
3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;
3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5--
dione;
3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-di-
one; a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane;
1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid,
bis(2,2,6,6-tetramethyl-4-piperidinyl) and
1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid,
bis(1,2,2,6,6-pentamethyl-4-piperidinyl);
N.sup.1-(.beta.-hydroxyethyl)3,3-pentamethylene-5,5-dimethylpiperazin-2-o-
ne; N.sup.1-tert-octyl-3,3,5,5-tetramethyl-diazepin-2-one;
N1-tert-octyl-3,3-pentamethylene-5,5-hexamethylene-diazepin-2-one;
N.sup.1-tert-octyl-3,3-pentamethylene-5,5-dimethylpiperazin-2-one;
trans-1,2-cyclohexane-bis-(N.sup.1-5,5-dimethyl-3,3-pentamethylene-2-pipe-
razinone;
trans-1,2-cyclohexane-bis-(N.sup.1-3,3,5,5-dispiropentamethylene-
-2-piperazinone);
N.sup.1-isopropyl-1,4-diazadispiro-(3,3,5,5)pentamethylene-2-piperazinone-
;
N.sup.1-isopropyl-1,4-diazadispiro-3,3-pentamethylene-5,5-tetramethylene-
-2-piperazinone;
N.sup.1-isopropyl-5,5-dimethyl-3,3-pentamethylene-2-piperazinone;
trans-1,2-cyclohexane-bis-N.sup.1-(dimethyl-3,3-pentamethylene-2-piperazi-
none);
N.sup.1-octyl-5,5-dimethyl-3,3-pentamethylene-1,4-diazepin-2-one;
and
N.sup.1-octyl-1,4-diazadispiro-(3,3,5,5)pentamethylene-1,5-diazepin-2-
-one. Other sterically hindered amines suitable for use with the
invention include, for example, any of those disclosed in EP 1 308
084.
[0139] The hindered amine light stabilizer can be present in an
amount from 0.01% to 10% by weight based on the total weight of the
polymer material to be stabilized (polyolefin). Preferably, the
amount of hindered amine is available from 0.05% to 5%, and more
preferably from 0.1% to 3% by weight based on the total weight of
the polymer material to be stabilized.
[0140] The light stabilizer can be an ultraviolet light absorber
chosen from a 2-hydroxybenzophenone, a
2-(2'-hydroxyphenyl)benzotriazole, a
2-(2'-hydroxyphenyl)-1,3,5-triazine, or mixtures thereof. In
particular, suitable light stabilizers can include one or more of
the following:
[0141] 2-(2'-Hydroxyphenyl)benzotriazoles, for example
2-(2'-hydroxy-5'-methylphenyl)-benzotriazole;
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole;
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole;
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole;
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole;
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole;
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole;
2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole;
2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole;
2-(3',5'-bis-(.alpha.,.alpha.-dimethylbenzyl)-2'-hydroxyphenyl)benzotriaz-
ole;
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chl-
oro-benzotriazole;
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-
-5-chloro-benzotriazole;
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-b-
enzotriazole;
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazo-
le;
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotr-
iazole;
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonyl]-2'-hydroxyphenyl-
)benzotriazole;
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole;
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole;
2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-y-
lphenol]; the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotr-
iazole with polyethylene glycol 300;
[R--CH.sub.2CH.sub.2--COO--CH.sub.2CH.sub.2].sub.2 where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl;
2-[2'-hydroxy-3'-(.alpha.,.alpha.-dimethylbenzyl)-5'-(1,1,3,3-tetramethyl-
butyl)-phenyl]benzotriazole; or
2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(.alpha.,.alpha.-dimethylb-
enzyl)-phenyl]benzotriazole;
[0142] 2-Hydroxybenzophenones, for example the 4-hydroxy,
4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, or
4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives;
[0143] Esters of substituted and unsubstituted benzoic acids, as
for example 4-tertbutyl-phenyl salicylate, phenyl salicylate,
octylphenyl salicylate, dibenzoyl resorcinol,
bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol,
2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate,
hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl
3,5-di-tert-butyl-4-hydroxybenzoate,
2-methyl-4,6-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate;
[0144] Nickel compounds, for example nickel complexes of
2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1
or 1:2 complex, with or without additional ligands such as
n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel
dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g.
the methyl or ethyl ester, of
4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes
of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecylketoxime,
nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or
without additional ligands; and
[0145] 2-(2'-hydroxyphenyl)-1,3,5-triazine compounds according to
Formula (VII):
##STR00016##
[0146] wherein each of R.sub.34 and R.sub.35 is independently
chosen from optionally substituted C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.10 hydrocarbyl-substituted amino, C.sub.1-C.sub.10
acyl or C.sub.1-C.sub.10 alkoxyl; and wherein R.sub.36 is present
at from 0 to 4 positions of the phenoxy portion of Formula (VII)
and in each instance is independently chosen from hydroxyl,
C.sub.1-C.sub.12 hydrocarbyl, C.sub.1-C.sub.12 alkoxyl,
C.sub.1-C.sub.12 alkoxyester, or C.sub.1-C.sub.12 acyl. Such
2-(2-hydroxyphenyl)-1,3,5-triazines include, but are not limited
to,
4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine
(CYASORB.RTM. 1164 available from Cytec Industries Inc.);
4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine;
2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;
2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazi-
ne;
2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dime-
thylphenyl)-s-triazine;
2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine-
;
2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazi-
ne; 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine;
2,4-bis(4-biphenylyl)-6-[2-hydroxy-4-[(octyloxycarbonyl)ethylideneoxy]phe-
nyl]-s-triazine;
2,4-bis(4-biphenylyl)-6-[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-s-triazine;
2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-h-
ydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine;
2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4(-3-benzyloxy-2-hydroxypropylox-
y)phenyl]-s-triazine;
2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triaz-
ine;
2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy-2-hydroxypropy-
loxy)-5-.alpha.-cumylphenyl]-s-triazine;
methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hy-
droxypropoxy)phenyl]-s-triazine}; methylene bridged dimer mixture
bridged in the 3:5', 5:5' and 3:3' positions in a 5:4:1 ratio;
2,4,6-tris(2-hydroxy-4-isooctyloxycarbonyliso-propylideneoxy-phenyl)-s-tr-
iazine;
2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-.alpha.-cumy-
lphenyl)-s-triazine;
2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyl-
oxy)phenyl]-s-triazine;
2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)-phenyl]-s-tria-
zine; mixture of
4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropox-
y)phenyl)-s-triazine and
4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-tridecyloxy-2-hydroxypropo-
xy)phenyl)-s-triazine (TINUVIN.RTM. 400 available from BASF Corp.);
4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4(3-(2-ethylhexyloxy)-2-hydroxy-
propoxy)-phenyl)-s-triazine;
4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine;
2-(4,6-Diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]pheno-
l (ADK STAB.RTM. LA-46 available from Adeka Palmarole, Saint-Louis,
France); 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine;
propanoic acid,
2,2',2''-[1,3,5-triazine-2,4,6-triyltris[(3-hydroxy-4,1-phenylene)o-
xy]]tris-1,1',1''-trioctyl ester (TINUVIN.RTM. 477 available from
BASF Corp.); propanoic acid,
2-[4-[4,6-bis([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2yl]-3-hydroxyphenoxyl]-
-isooctyl ester (TINUVIN.RTM. 479 available from BASF Corp.); or
mixtures thereof.
[0147] In certain embodiments, the stabilized polymer compositions
according to the invention include a blend of at least one hindered
amine light stabilizer and at least one ultraviolet light
absorber.
[0148] Further embodiments of the stabilized polymer compositions
according to the invention include at least one compound chosen
from: [0149] (i) a hydroxylamine compound according to Formula
(VIII):
##STR00017##
[0150] wherein
[0151] T.sub.1 is chosen from an optionally substituted
C.sub.1-C.sub.36 hydrocarbyl, C.sub.5-C.sub.12 cycloalkyl, or
C.sub.7-C.sub.9 aralkyl; and
[0152] T.sub.2 is chosen from hydrogen or T1; or [0153] a tertiary
amine oxide compound according to Formula (IX):
##STR00018##
[0154] wherein
[0155] each of W.sub.1 and W.sub.2 is independently a
C.sub.6-C.sub.36 hydrocarbyl chosen from a straight or branched
chain C.sub.6-C.sub.36 alkyl, C.sub.6-C.sub.12 aryl,
C.sub.7-C.sub.36 aralkyl, C.sub.7-C.sub.36 alkaryl,
C.sub.5-C.sub.36 cycloalkyl, C.sub.6-C.sub.36 alkcycloalkyl, or
C.sub.6-C.sub.36 cycloalkylalkyl;
[0156] W.sub.3 is a C.sub.1-C.sub.36 hydrocarbyl chosen from
straight or branched chain C.sub.1-C.sub.36 alkyl, C.sub.6-C.sub.12
aryl, C.sub.7-C.sub.36 aralkyl, C.sub.7-C.sub.36 alkaryl,
C.sub.5-C.sub.36 cycloalkyl, C.sub.6-C.sub.36 alkcycloalkyl; or
C.sub.6-C.sub.36 cycloalkylalkyl;
[0157] with the proviso that at least one of W.sub.1, W.sub.2 and
W.sub.3 contains a R carbon-hydrogen bond; and
[0158] wherein said alkyl, aralkyl, alkaryl, cycloalkyl,
alkcycloalkyl and cycloalkylalkyl groups of W.sub.1, W.sub.2 and
W.sub.3 may be interrupted by from one to sixteen groups chosen
from --O--, --S--, --SO--, --SO.sub.2--, --COO--, --OCO--, --CO--,
--NW.sub.4--, --CONW.sub.4-- or --NW.sub.4CO--, or
[0159] wherein said alkyl, aralkyl, alkaryl, cycloalkyl,
alkcycloalkyl and cycloalkylalkyl groups of W.sub.1, W.sub.2 and
W.sub.3 are substituted with from one to sixteen groups chosen from
--OW.sub.4, --SW.sub.4, --COOW.sub.4, --OCOW.sub.4, --COW.sub.4,
--N(W.sub.4).sub.2, --CON(W.sub.4).sub.2, --NW.sub.4COW.sub.4 and
5- and 6-membered rings containing the group
--C(CH.sub.3)(CH.sub.2R.sub.x)NL(CH.sub.2R.sub.x)(CH.sub.3)C--;
and
[0160] wherein
[0161] W.sub.4 is chosen from hydrogen or C.sub.1-C.sub.8
alkyl;
[0162] R.sub.x is chosen from hydrogen or methyl; and
[0163] L is chosen from C.sub.1-C.sub.30 alkyl, --C(O)R or --OR,
wherein R is C.sub.1-C.sub.30 straight or branched chain alkyl;
or
[0164] wherein said alkyl, aralkyl, alkaryl, cycloalkyl,
alkcycloalkyl and cycloalkylalkyl groups of W.sub.1, W.sub.2 and
W.sub.3 are both interrupted and substituted by any of the groups
mentioned above; or
[0165] wherein said aryl groups of W.sub.1, W.sub.2 and W.sub.3 are
substituted with from one to three substituents independently
chosen from halogen, C.sub.1-C.sub.8 alkyl or C.sub.1-C.sub.8
alkoxy; or (iii) mixtures of (i) and (ii).
[0166] In particular embodiments, preference is given to
N,N-dihydrocarbylhydroxylamine compounds according to Formula
(VIII) wherein T.sub.1 and T.sub.2 are independently chosen from
benzyl, ethyl, octyl, lauryl, dodecyl, tetradecyl, hexadecyl,
heptadecyl or octadecyl; or wherein T.sub.1 and T are each the
alkyl mixture found in hydrogenated tallow amine.
[0167] In certain embodiments, hydroxylamine compounds according to
Formula (VIII) are chosen from: N,N-dibenzylhydroxylamine;
N,N-diethylhydroxylamine; N,N-dioctylhydroxylamine;
N,N-dilaurylhydroxylamine; N,N-didodecylhydroxylamine;
N,N-ditetradecylhydroxylaamine; N,N-dihexadecylhydroxylamine;
N,N-dioctadecylhydroxylamine;
N-hexadecyl-N-tetradecylhydroxylamine;
N-hexadecyl-N-heptadecylhydroxylamine;
N-hexadecyl-N-octadecylhydroxylamine;
N-heptadecyl-N-octadecylhydroxylamine; N,N-di(hydrogenated
tallow)hydroxylamine; or N,N-di(alkyl)hydroxylamine produced by the
direct oxidation of N,N-di(hydrogenated tallow)amine.
[0168] In certain embodiments, preference is given to those
structures of Formula (IX) where W.sub.1 and W.sub.2 are
independently benzyl or substituted benzyl. It is also possible for
each of W.sub.1, W.sub.2, and W.sub.3 to be the same residue. In
other embodiments, W.sub.1 and W.sub.2 can be alkyl groups of 8 to
26 carbon atoms, more preferably alkyl groups of 10 to 26 carbon
atoms. W.sub.3 can be an alkyl group of 1 to 22 carbon atoms, more
preferably methyl or substituted methyl. Other preferred amine
oxides include those wherein W.sub.1, W.sub.2, and W.sub.3 are the
same alkyl groups of 6 to 36 carbon atoms. Preferably, all of the
aforementioned residues for W.sub.1, W.sub.2, and W.sub.3 are
saturated hydrocarbon residues or saturated hydrocarbon residues
containing at least one of the aforementioned --O--, --S--, --SO--,
--COO--, --CO--, or --CONW.sub.4-- moieties. Those skilled in the
art will be able to envision other useful residues for each of
W.sub.1, W.sub.2, and W.sub.3 without detracting from the present
invention.
[0169] The saturated amine oxides may also include poly(amine
oxides). By poly(amine oxide) is meant tertiary amine oxides
containing at least two tertiary amine oxides per molecule.
Illustrative poly(amine oxides), also called "poly(tertiary amine
oxides)", include, but are not limited to, the tertiary amine oxide
analogues of aliphatic and alicyclic diamines such as, for example,
1,4-diaminobutane; 1,6-diaminohexane; 1,10-diaminodecane; and
1,4-diaminocyclohexane, and aromatic based diamines such as, for
example, diamino anthraquinones and diaminoanisoles.
[0170] Suitable amine oxides for use with the invention also
include tertiary amine oxides derived from oligomers and polymers
of the aforementioned diamines. Useful amine oxides also include
amine oxides attached to polymers, for example, polyolefins,
polyacrylates, polyesters, polyamides, polystyrenes, and the like.
When the amine oxide is attached to a polymer, the average number
of amine oxides per polymer can vary widely as not all polymer
chains need to contain an amine oxide. All of the aforementioned
amine oxides may optionally contain at least one --O--, --S--,
--SO--, --CO.sub.2--, --CO--, or --CONW.sub.4-- moiety. In a
preferred embodiment, each tertiary amine oxide of the polymeric
tertiary amine oxide contains a C.sub.1 residue.
[0171] The groups W.sub.1, W.sub.2 and W.sub.3 of Formula (IX) may
be attached to a molecule containing a hindered amine. Hindered
amines are known in the art and the amine oxide of the present
invention may be attached to the hindered amine in any manner and
structural position of the hindered amine. Useful hindered amines
when part of an amine oxide compound include those of the general
Formulas (X) and (XI):
##STR00019##
[0172] wherein L and R.sub.x are defined as described above.
[0173] Also included are amine oxides containing more than one
hindered amine and more than one saturated amine oxide per
molecule. The hindered amine may be attached to a poly(tertiary
amine oxide) or attached to a polymeric substrate, as discussed
above.
[0174] The hydroxyl amine derivatives and/or amine oxide
derivatives can be used in amounts, in total, of about 0.0005% to
about 5%, in particular from about 0.001% to about 2%, typically
from about 0.01% to about 2% by weight, based on the weight of the
polyolefin.
[0175] In other embodiments, the stabilized polymer composition
(polyolefin) includes further optional co-additives chosen from
nucleating agents, fillers, reinforcing agents, polymer additives
or mixtures thereof.
[0176] Examples of such co-additives include, but are not limited
to:
[0177] Basic co-additives, for example, melamine,
polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea
derivatives, hydrazine derivatives, amines, polyamides,
polyurethanes, alkali metal salts and alkaline earth metal salts of
higher fatty acids for example calcium stearate, zinc stearate,
magnesium behenate, magnesium stearate, sodium ricinoleate and
potassium palmitate, antimony pyrocatecholate or zinc
pyrocatecholate; In some embodiments, the basic co-additive (iii)
is at least one of calcium stearate, zinc stearate, magnesium
behenate, magnesium stearate, sodium ricinoleate or potassium
palmitate.
[0178] Nucleating agents, for example, inorganic substances such as
talcum, metal oxides such as titanium dioxide or magnesium oxide,
phosphates, carbonates or sulfates of, preferably, alkaline earth
metals; organic compounds such as mono- or polycarboxylic acids and
the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid,
diphenylacetic acid, sodium succinate or sodium benzoate; polymeric
compounds such as ionic copolymers (ionomers);
[0179] Fillers and reinforcing agents, for example, calcium
carbonate, silicates, glass fibres, glass bulbs, asbestos, talc,
kaolin, mica, barium sulfate, metal oxides and hydroxides (e.g.,
aluminium hydroxide or magnesium hydroxide, carbon black, graphite,
wood flour and flours or fibers of other natural products,
synthetic fibers; impact modifiers
[0180] Benzofuranones and indolinones, for example those disclosed
in U.S. Pat. Nos. 4,325,863; 4,338,244; 5,175,312; 5,216,052;
5,252,643; 5,369,159; 5,488,117; 5,356,966; 5,367,008; 5,428,162;
5,428,177; 5,516,920; DE-A-4316611; DE-A-4316622; DE-A-4316876;
EP-A-0589839 or EP-A-0591102 or
3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,
5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,
3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one]-
, 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,
3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,
3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,
3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,
3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one;
[0181] Metal deactivators, for example N,N'-diphenyloxamide,
N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,
3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl
dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl
bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide,
N,N'-bis(salicyloyl)oxalyl dihydrazide,
N,N'-bis(salicyloyl)thiopropionyl dihydrazide;
[0182] Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,
N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,
N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone,
N-hexadecyl-alpha-pentadecyl-nitrone,
N-octadecyl-alpha-heptadecyl-nitrone,
N-hexadecyl-alpha-heptadecyl-nitrone,
N-ocatadecyl-alpha-pentadecyl-nitrone,
N-heptadecyl-alpha-heptadecyl-nitrone,
N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from
N,N-di(hydrogenated tallow)hydroxylamine;
[0183] Thiosynergists, for example, dilauryl thiodipropionate or
distearyl thiodipropionate; and/or
[0184] Peroxide scavengers, for example esters of
.beta.-thiodipropionic acid, for example the lauryl, stearyl,
myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt
of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate,
dioctadecyl disulfide, pentaerythritol
tetrakis(.beta.-dodecylmercapto)propionate.
[0185] Other additives include, for example, plasticisers,
lubricants, emulsifiers, pigments, rheology additives, catalysts,
flow-control agents, optical brighteners, flameproofing agents,
antistatic agents, clarifying agents and blowing agents.
[0186] In masterbatch compositions, the stabilizer composition is
present from 0.001% to 65.0% by weight based on the total weight of
the masterbatch composition, and the amount is based on the number
and type of stabilizing additives being added and/or the
characteristics of the polymer composition to be stabilized. In
some embodiments, the stabilizer composition is present from 0.01%
to 50% by weight of the total weight of the masterbatch
composition, and preferably from 0.05% to 25% by weight of the
total, or from 0.1% to 10% by weight of the total. Those of
ordinary skill in the art will be able to readily determine the
amount and type of stabilizing additive(s) that should be added
based on preparations as known and/or described in the literature,
or through no more than routine experimentation.
[0187] The stabilized polymer compositions according to the
invention can be readily made by any suitable method known to those
of skill in the art. In certain embodiments, the components of the
stabilized polymer compositions are mixed by at least one technique
chosen from extruding, pelletizing, grinding, and molding. In other
embodiments, mixing can be performed by at least one of melting,
dissolution in a solvent, and dry mixing.
[0188] The incorporation of components for the stabilizer
composition and optional further additives into the polymer
composition is carried out by any suitable method known to those of
skill in the art, for example before or after molding or also by
applying the dissolved or dispersed stabilizer mixture to the
polyolefin, with or without subsequent evaporation of the solvent.
The stabilizer components and optional further additives can also
be added to the polymer compositions to be stabilized in the form
of a masterbatch.
[0189] Components of the stabilizer composition and optional
further additives can also be added before or during the
polymerization or before crosslinking. They can also be
incorporated into the polymer composition to be stabilized in pure
form (i.e., neat and directly to the resin) or encapsulated in
waxes, oils or polymers. Various additives can also be preblended
(i.e., mixed together) for simple addition to the polymer
compositions to be stabilized. Components of the stabilizer
composition and optional further additives can also be sprayed onto
the polymer compositions to be stabilized. They are able to dilute
other additives (for example the conventional additives indicated
above) or their melts so that they can be sprayed also together
with these additives onto the polymer compositions to be
stabilized. In the case of spherically polymerized polymers it may,
for example, be advantageous to apply components of the stabilizer
composition optionally together with other additives, by
spraying.
[0190] It is also contemplated that the components of the
stabilizer compositions and/or polymer compositions described
herein may be contained in a kit. The kit may include single or
multiple components of at least one stabilizer composition
according to the invention, at least one polymer composition
according to the invention, and at least one further optional
additive, each packaged or formulated individually, or single or
multiple components of at least one stabilizer composition
according to the invention, at least one polymer composition
according to the invention, and at least one further optional
additive packaged or formulated in combination. Thus, one or more
components of a stabilizer composition can be present in first
container, and the kit can optionally include one or more
components of the stabilizer composition and/or polymer composition
in a second or further container. The container or containers are
placed within a package, and the package can optionally include
administration or mixing instructions in the form of a label or
website address on the package, or in the form of an insert
included in the packaging of the kit. A kit can include additional
components or other means for administering or mixing the
components as well as solvents or other means for formulation.
[0191] As can be seen from the following examples, the polyolefin,
chroman-based compound, phosphite or phosphonite, and at least one
basic co-additive, and amounts of the chroman-based compound,
phosphite or phosphonite, and at least one basic co-additive can be
selected so that the polyolefin remains stable and retains its
optimal mechanical and/or physical properties over a longer period
of time in the oven, even in the absence of a sterically hindered
amine light stabilizer (HALS).
[0192] As can be further seen from the following examples, the
polyolefin, chroman-based compound, phosphite or phosphonite, and
at least one basic co-additive, and amounts of the chroman-based
compound, phosphite or phosphonite, and at least one basic
co-additive can be selected so that at least one of the following
results are obtained in a rotational molding operation employed to
produce the polymeric hollow article, even in the absence of a
sterically hindered amine light stabilizer (HALS):
[0193] a maximum mean failure energy (MFE) of the polymeric article
is reached at a shorter time interval;
[0194] a higher MFE of the polymeric article is retained over a
longer heating time; or
[0195] a processing window is enlarged to a peak internal air
temperature (PIAT) of up to 452.degree. F. with yellowness index of
the article remaining substantially unchanged up to a PIAT of
452.degree. F.
[0196] Notably, these results were obtained, even in the absence of
sterically hindered amine light stabilizers (HALS), for example in
the absence of secondary HALS as disclosed in U.S. Patent
Publication No. 2009/0085252 A1. These results were also obtained,
even in the absence of antistatic agents, for example in the
absence of the ethoxylated amines and ethoxylated amides as
disclosed in U.S. Patent Application Publication No. 2006/0167146
A1.
Embodiments
[0197] Embodiment 1. A polymeric hollow article made by a process
comprising:
[0198] a) filling a mold with a polyolefin and a stabilizing amount
of a stabilizer composition, wherein the stabilizer composition
comprises: [0199] (i) at least one chroman-based compound according
to Formula (V): wherein
##STR00020##
[0200] R.sub.21 is present at from 1 to 4 positions of the aromatic
portion of Formula (V) and in each instance is independently chosen
from: [0201] C.sub.1-C.sub.12 hydrocarbyl; [0202] NR'R'', wherein
each of R' and R'' is independently chosen from H or
C.sub.1-C.sub.12 hydrocarbyl; or [0203] OR.sub.27, wherein R.sub.27
is chosen from C.sub.1-C.sub.12 hydrocarbyl, COR''' or
Si(R.sub.28).sub.3, wherein R''' is chosen from H or
C.sub.1-C.sub.20 hydrocarbyl and R.sub.28 is chosen from
C.sub.1-C.sub.12 hydrocarbyl or alkoxy; and wherein at least one
instance of R.sub.21 is OR.sub.27;
[0204] R.sub.22 is chosen from H or C.sub.1-C.sub.12
hydrocarbyl;
[0205] R.sub.23 is chosen from H or C.sub.1-C.sub.20
hydrocarbyl;
[0206] each of R.sub.24-R.sub.25 is independently chosen from H,
C.sub.1-C.sub.12 hydrocarbyl or OR'''', wherein R'''' is chosen
from H or C.sub.1-C.sub.12 hydrocarbyl; and
[0207] R.sub.26 is H or a bond which together with R.sub.25 forms
.dbd.O; [0208] (ii) at least one phosphite or phosphonite; and
[0209] (iii) a basic co-additive selected from alkali metal or
alkaline metal salts of higher fatty acids;
[0210] b) rotating the mold around at least one axis while heating
the mold in an oven, thereby fusing the composition and spreading
it to the walls of the mold;
[0211] c) cooling the mold; and
[0212] d) opening the mold to remove the resulting product,
thereby producing the polymeric hollow article.
[0213] Embodiment 2. A polymeric hollow article according to
embodiment 1, wherein the at least one phosphite or phosphonite is
chosen from:
[0214] (i) a compound according to Formulas (1)-(7):
##STR00021##
in which the indices are integral and
[0215] n is 2, 3 or 4; p is 1 or 2; q is 2 or 3; y is 1, 2 or 3;
and z is 1 to 6;
[0216] A.sub.1, if n or q is 2, is C.sub.2-C.sub.18 alkylene;
C.sub.2-C.sub.12 alkylene interrupted by oxygen, sulfur or
--NR.sub.4--; a radical of the formula
##STR00022##
or phenylene;
[0217] A.sub.1, if n or q is 3, is a trivalent radical of the
formula C.sub.rH.sub.2r-1; wherein r is an integer from 4 to
12;
[0218] A.sub.1, if n is 4, is
##STR00023##
[0219] B is a direct bond, --CH.sub.2--, --CHR.sub.4--,
--CR.sub.1R.sub.4--, sulfur, C.sub.5-C.sub.7 cycloalkylidene, or
cyclohexylidene which is substituted by from 1 to 4 C.sub.1-C.sub.4
alkyl radicals in position 3, 4 and/or 5;
[0220] D.sub.1, if p is 1, is C.sub.1-C.sub.4 alkyl and, if p is 2,
is --CH.sub.2OCH.sub.2--;
[0221] D.sub.2, if p is 1, is C.sub.1-C.sub.4 alkyl;
[0222] E, if y is 1, is C.sub.1-C.sub.18 alkyl, --OR.sub.1 or
halogen;
[0223] E, if y is 2, is --O-A.sub.2-O--, wherein A.sub.2 is as
defined for A.sub.1 when n is 2;
[0224] E, if y is 3, is a radical of the formula
R.sub.4C(CH.sub.2O--).sub.3 or N(CH.sub.2CH.sub.2O--).sub.3;
[0225] Q is the radical of an at least z-valent mono- or
poly-alcohol or phenol, this radical being attached via the oxygen
atom of the OH group of the mono- or poly-alcohol or phenol to the
phosphorus atom;
[0226] R.sub.1, R.sub.2 and R.sub.3 independently of one another
are C.sub.1-C.sub.18 alkyl which is unsubstituted or substituted by
halogen, --COOR.sub.4, --CN or --CONR.sub.4R.sub.4;
C.sub.2-C.sub.18 alkyl interrupted by oxygen, sulfur or
--NR.sub.4--; C.sub.7-C.sub.9 phenylalkyl; C.sub.5-C.sub.12
cycloalkyl, phenyl or naphthyl; naphthyl or phenyl substituted by
halogen, 1 to 3 alkyl radicals or alkoxy radicals having a total of
1 to 18 carbon atoms or by C.sub.7-C.sub.9 phenylalkyl; or a
radical of the formula
##STR00024##
in which m is an integer from the range 3 to 6;
[0227] R.sub.4 is hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.5-C.sub.12
cycloalkyl or C.sub.7-C.sub.9 phenylalkyl,
[0228] R.sub.5 and R.sub.6 independently of one another are
hydrogen, C.sub.1-C.sub.8 alkyl or C.sub.5-C.sub.6 cycloalkyl,
[0229] R.sub.7 and R.sub.8, if q is 2, independently of one another
are C.sub.1-C.sub.4 alkyl or together are a
2,3-dehydropentamethylene radical;
[0230] R.sub.7 and R.sub.8, if q is 3, are methyl;
[0231] each instance of R.sub.14 is independently hydrogen,
C.sub.1-C.sub.9 alkyl or cyclohexyl;
[0232] each instance of R.sub.15 is independently hydrogen or
methyl;
[0233] X and Y are each a direct bond or oxygen;
[0234] Z is a direct bond, methylene, --C(R.sub.16).sub.2-- or
sulfur; and
[0235] R.sub.16 is C.sub.1-C.sub.8 alkyl;
[0236] (ii) a trisarylphosphite according to Formula 8:
##STR00025##
wherein R.sub.17 is a substituent that is present at from 0 to 5
positions of the aromatic portion of Formula (8) and in each
instance is independently chosen from C.sub.1-C.sub.20 alkyl,
C.sub.3-C.sub.20 cycloalkyl, C.sub.4-C.sub.20 alkyl cycloalkyl,
C.sub.6-C.sub.10 aryl or C.sub.7-C.sub.20 alkylaryl; or
[0237] (iii) mixtures of (i) and (ii).
[0238] Embodiment 3. A polymeric hollow article according to
embodiment 1 or 2, wherein the phosphite or phosphonite is chosen
from triphenyl phosphite; diphenyl alkyl phosphites; phenyl dialkyl
phosphites; trilauryl phosphite; trioctadecyl phosphite; distearyl
pentaerythritol phosphite; tris(2,4-di-t-butylphenyl) phosphite;
tris(nonylphenyl) phosphite; a compound of formulae (A), (B), (C),
(D), (E), (F), (G), (H), (J), (K) or (L):
##STR00026## ##STR00027##
2-butyl-2-ethyl-1,3-propanediol 2,4,6-tri-t-butylphenol phosphite;
bis-(2,6-di-t-butyl-4-methlphenyl) pentaerythritol diphosphite;
2-butyl-2-ethyl-1,3-propanediol 2,4-di-cumylphenol phosphite;
2-butyl-2-ethyl-1,3-propanediol 4-methyl-2,6-di-t-butylphenol
phosphite or bis-(2,4,6-t-butyl-phenyl) pentaerythritol
diphosphite.
[0239] Embodiment 4. A polymeric hollow article according to any of
embodiments 1 to 3, wherein the at least one phosphite or
phosphonite is chosen from tris(2,4-di-t-butylphenyl)phosphite
(IRGAFOS.RTM. 168); bis(2,4-dicumylphenyl)pentaerythritol
diphosphite (DOVERPHOS.RTM. S9228) or
tetrakis(2,4-di-t-butylphenyl)4,4'-biphenylene-diphosphonite
(IRGAFOS.RTM. P-EPQ).
[0240] Embodiment 5. A polymeric hollow article according to any of
embodiments 1 to 4, wherein the stabilizer composition further
comprises at least one hindered phenol.
[0241] Embodiment 6. A polymeric hollow article according to
embodiment 5, wherein the at least one hindered phenol comprises a
molecular fragment according to one or more of Formula (IVa),
(IVb), or (IVc):
##STR00028##
wherein
[0242] R.sub.18 of Formula (IVa), (IVb), or (IVc) is independently
chosen from hydrogen or a C.sub.1-4 hydrocarbyl;
[0243] each of R.sub.19 and R.sub.20 of Formula (IVa), (IVb), or
(IVc) is independently chosen from hydrogen or a C.sub.1-C.sub.20
hydrocarbyl; and
[0244] R.sub.37 of Formula (IVa), (IVb), or (IVc) is independently
chosen from a C.sub.1-C.sub.12 hydrocarbyl.
[0245] Embodiment 7. A polymeric hollow article according to
embodiment 6, wherein R.sub.18 and R.sub.37 are chosen from methyl
or t-butyl.
[0246] Embodiment 8. A polymeric hollow article according to any of
embodiments 5 to 7, wherein the at least one hindered phenol
compound is chosen from
(1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6--
(1H,3H,5H)-trione;
1,1,3-tris(2'-methyl-4'-hydroxy-5'-t-butylphenyl)butane;
triethylene glycol
bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate];
4,4'-thiobis(2-t-butyl-5-methylphenol); 2,2'-thiodiethylene
bis[3-(3-t-butyl-4-hydroxyl-5-methylphenyl)propionate]; octadecyl
3-(3'-t-butyl-4'-hydroxy-5'-methylphenyl)propionate;
tetrakismethylene(3-t-butyl-4-hydroxy-5-methylhydrocinnamate)methane;
N,N'-hexamethylene
bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionamide];
di(4-t-butyl-3-hydroxy-2,6-dimethyl benzyl) thiodipropionate;
octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate; or mixtures
thereof.
[0247] Embodiment 9. A polymeric hollow article according to any of
embodiments 1 to 8, wherein R.sub.21 is present in at least one
instance as OR.sub.27.
[0248] Embodiment 10. A polymeric hollow article according to any
of embodiments 1 to 9, wherein R.sub.21 is present in at least
three instances and is chosen from OR.sub.27 or methyl.
[0249] Embodiment 11. A polymeric hollow article according to any
of embodiments 1 to 10, wherein R.sub.23 is a C.sub.1-C.sub.18
hydrocarbyl.
[0250] Embodiment 12. A polymeric hollow article according to any
of embodiments 1 to 11, wherein the chroman-based compound is
vitamin E acetate according to Formula (Va)
##STR00029##
wherein R.sub.21 is --OC(O)CH.sub.3.
[0251] Embodiment 13. A polymeric hollow article according to any
of embodiments 1 to 12, wherein the chroman-based compound
comprises two or more compounds according to Formula (V).
[0252] Embodiment 14. A polymeric hollow article according to any
of embodiments 1 to 13, wherein the chroman-based compound is
present from 0.001% to 5.0% by weight of the weight of the
polyolefin.
[0253] Embodiment 15. A polymeric hollow article according to
embodiment 14, wherein the chroman-based compound is present from
0.01% to 1.0% by weight of the weight of the polyolefin.
[0254] Embodiment 16. A polymeric hollow article according to any
of embodiments 1 to 15, wherein the polyolefin is chosen from:
[0255] (i) polymers of monoolefins chosen from polypropylene,
polyisobutylene, polybut-1-ene, or poly-4-methylpent-1-ene;
[0256] (ii) polymers of diolefins chosen from polyisoprene or
polybutadiene;
[0257] (iii) polymers of cycloolefins chosen from cyclopentene or
norbornene;
[0258] (iv) polyethylene chosen from optionally crosslinked
polyethylene, high density polyethylene (HDPE), high density and
high molecular weight polyethylene (HDPE-HMW), high density and
ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density
polyethylene (MDPE), low density polyethylene (LDPE), linear low
density polyethylene (LLDPE), very low density polyethylene
(VLDPE), or ultralow density polyethylene (ULDPE);
[0259] (v) copolymers of the monoolefins, diolefins, or
cycloolefins of any of (i) to (iv); or
[0260] vi) mixtures of any of (i) to (v).
[0261] Embodiment 17. A polymeric hollow article according to any
of embodiments 1 to 16, wherein the polyolefin is at least one of
linear low density polyethylene (LLDPE), medium density
polyethylene (MDPE), high density polyethylene (HDPE), or
polypropylene.
[0262] Embodiment 18. A polymeric hollow article according to any
of embodiments 1 to 17, wherein the stabilizer composition further
comprises a light stabilizer chosen from hindered amine light
stabilizers, hindered hydroxyl benzoates, nickel phenolates,
ultraviolet light stabilizers, or mixtures thereof, in an amount
effective to stabilize the polymer composition against the
degradative effects of visible and/or ultraviolet light
radiation.
[0263] Embodiment 19. A polymeric hollow article according to
embodiment 18, wherein the light stabilizer is a hindered amine
light stabilizer comprising a molecular fragment according to:
[0264] (i) Formula (VI):
##STR00030##
[0265] wherein
[0266] R.sub.31 is chosen from hydrogen, OH, C.sub.1-C.sub.20
hydrocarbyl, --CH.sub.2CN, C.sub.1-C.sub.12 acyl or
C.sub.1-C.sub.18 alkoxy;
[0267] R.sub.38 is chosen from hydrogen or C.sub.1-C.sub.8
hydrocarbyl; and
[0268] each of R.sub.29, R.sub.30, R.sub.31, and R.sub.32 is
independently chosen from a C.sub.1-C.sub.20 hydrocarbyl; or
R.sub.60 and R.sub.61 and/or R.sub.63 and R.sub.64 taken together
with the carbon to which they are attached form a C.sub.5-C.sub.10
cycloalkyl; or
[0269] (ii) Formula (VIa)
##STR00031##
[0270] wherein
[0271] m is an integer from 1 to 2;
[0272] R.sub.39 is chosen from hydrogen, OH, C.sub.1-C.sub.20
hydrocarbyl, --CH.sub.2CN, C.sub.1-C.sub.12 acyl or
C.sub.1-C.sub.18 alkoxy; and
[0273] each of G.sub.1-G.sub.4 is independently a C.sub.1-C.sub.20
hydrocarbyl.
[0274] Embodiment 20. A polymeric hollow article according to
embodiment 19, wherein the hindered amine light stabilizer is
chosen from bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate;
bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl
3,5-di-tert-butyl-4-hydroxybenzylmalonate; a condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid; 2,2,6,6-tetramethylpiperidin-4-yl stearate;
2,2,6,6-tetramethylpiperidin-4-yl dodecanate;
1,2,2,6,6-pentamethylpiperidin-4-yl stearate;
1,2,2,6,6-pentamethylpiperidin-4-yl dodecanate; a condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine;
tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate;
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylat-
e; 4-benzoyl-2,2,6,6-tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-bu-
tylbenzyl)malonate;
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate; a condensate
of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine
and 4-morpholino-2,6-dichloro-1,3,5-triazine; a condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane; a condensate of
2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis-(3-aminopropylamino)ethane;
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d-
ione;
3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;
3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5--
dione;
3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-di-
one; a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine; a condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; a condensate of
1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine
and 4-butylamino-2,2,6,6-tetramethylpiperidine;
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane;
oxo-piperanzinyl-triazines; a reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
and epichlorohydrin; tetrakis(2,2,6,6-tetramethyl-4-piperidyl)
butane-1,2,3,4-tetracarboxylate; 1,2,3,4-butanetetracarboxylic
acid, tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl)ester;
1,2,3,4-butanetetracarboxylic acid,
1,2,2,6,6-pentamethyl-4-piperdinyl tridecyl ester;
1,2,3,4-butanetetracarboxylic acid,
2,2,6,6-tetramethyl-4-piperidinyl tridecyl ester;
1,2,3,4-butanetetracarboxylic acid, polymer with
2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]-undecane-3,9-diethanol,1,-
2,2,6,6-pentamethyl-4-piperdinyl ester;
1,2,3,4-butanetetracarboxylic acid, polymer with
2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]-undecane-3,9-diethanol,
2,2,6,6-tetramethyl-4-piperdinyl ester;
bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate;
1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-piperdinol;
1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperi-
dine;
1-(4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-octadec-
anoyloxy-2-methylpropane;
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperdinol; a reaction
product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperdinol and
dimethylsuccinate;
2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one;
the ester of 2,2,6,6-tetramethyl-4-piperidinol with higher fatty
acids;
3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione;
1H-Pyrrole-2,5-dione, 1-octadecyl-, polymer with
(1-methylethenyl)benzene and
1-(2,2,6,6-tetramethyl-4-piperidinyl)-1H-pyrrole-2,5-dione;
piperazinone,
1,1',1''-[1,3,5-triazine-2,4,6-triyltris[(cyclohexylimino)-2,1-ethanediyl-
]]tris[3,3,5,5-tetramethyl-; piperazinone,
1,1',1''-[1,3,5-triazine-2,4,6-triyltris[(cyclohexylimino)-2,1-ethanediyl-
]]tris[3,3,4,5,5-pentamethyl-; the reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
and epichlorohydrin; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; the condensate of
1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine
and 4-butylamino-2,2,6,6-tetramethylpiperidine; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine; the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane; the condensate of
2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis-(3-aminopropylamino)ethane;
2-[(2-hydroxyethyl)amino]-4,6-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylp-
iperidin-4-yl)butylamino-1,3,5-triazine; propanedioic acid,
[(4-methoxyphenyl)-methylene]-bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)
ester;
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracar-
boxylate; benzenepropanoic acid,
3,5-bis(1,1-dimethylethyl)-4-hydroxy-,
1-[2-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]ethyl]--
2,2,6,6-tetramethyl-4-piperidinyl ester;
N-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N'-dodecyloxalamide;
tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate;
1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid,
bis(1,2,2,6,6-pentamethyl-4-piperidinyl):
1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid,
bis(2,2,6,6-tetramethyl-4-piperidinyl); the condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine;
1,2,3,4-butanetetracarboxylic acid,
1,2,2,6,6-pentamethyl-4-piperidinyl tridecyl ester;
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylat-
e; 1,2,3,4-butanetetracarboxylic acid,
2,2,6,6-tetramethyl-4-piperidinyl tridecyl ester;
tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxyl-
ate; mixture of
2,2,4,4-tetramethyl-21-oxo-7-oxa-3.20-diazaspiro(5.1.11.2)-heneicosane-20-
-propanoic acid-dodecylester and
2,2,4,4-tetramethyl-21-oxo-7-oxa-3.20-diazaspiro(5.1.11.2)-heneicosane-20-
-propanoic acid-tetradecylester;
1H,4H,5H,8H-2,3a,4a,6,7a,8a-hexaazacyclopenta[def]fluorene-4,8-dione,
hexahydro-2,6-bis(2,2,6,6-tetramethyl-4-piperidinyl)-;
polymethyl[propyl-3-oxy(2',2',6',6'-tetramethyl-4,4'-piperidinyl)]siloxan-
e;
polymethyl[propyl-3-oxy(1',2',2',6',6'-pentamethyl-4,4'-piperidinyl)]si-
loxane; copolymer of methylmethacrylate with ethyl acrylate and
2,2,6,6-tetramethylpiperidin-4-yl acrylate; copolymer of mixed
C.sub.20 to C.sub.24 alpha-olefins and
(2,2,6,6-tetramethylpiperidin-4-yl)succinimide;
1,2,3,4-butanetetracarboxylic acid, polymer with
.beta.,.beta.,.beta.',.beta.'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]unde-
cane-3,9-diethanol, 1,2,2,6,6-pentamethyl-4-piperidinyl ester;
1,2,3,4-butanetetracarboxylic acid, polymer with
.beta.,.beta.,.beta.',.beta.'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]unde-
cane-3,9-diethanol, 2,2,6,6-tetramethyl-4-piperidinyl ester
copolymer; 1,3-benzenedicarboxamide,
N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl;
1,1'-(1,10-dioxo-1,10-decanediyl)-bis(hexahydro-2,2,4,4,6-pentamethylpyri-
midine; ethane diamide,
N-(1-acetyl-2,2,6,6-tetramethylpiperidinyl)-N'-dodecyl; formamide,
N,N'-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl);
D-glucitol,
1,3:2,4-bis-O-(2,2,6,6-tetramethyl-4-piperidinylidene)-;
2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane;
propanamide,
2-methyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)-2-[(2,2,6,6-tetramethyl-4--
piperidinyl)amino]-;
7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-20-propanoic acid,
2,2,4,4-tetramethyl-21-oxo-, dodecyl ester;
N-(2,2,6,6-tetramethylpiperidin-4-yl)-.beta.-aminopropionic acid
dodecyl ester;
N-(2,2,6,6-tetramethylpiperidin-4-yl)-N'-aminooxalamide;
propanamide,
N-(2,2,6,6-tetramethyl-4-piperidinyl)-3-[(2,2,6,6-tetramethyl-4-piperidin-
yl)amino]-; mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione;
3-dodecyl-1-(1-ethanoyl-2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-
-dione; bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl
3,5-di-tert-butyl-4-hydroxybenzylmalonate;
tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate;
1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone);
4-benzoyl-2,2,6,6-tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-bu-
tylbenzyl)malonate;
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate;
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d-
ione;
3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;
3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5--
dione;
3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-di-
one; a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane;
1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid,
bis(2,2,6,6-tetramethyl-4-piperidinyl) and
1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid,
bis(1,2,2,6,6-pentamethyl-4-piperidinyl);
N.sup.1-(.beta.-hydroxyethyl)3,3-pentamethylene-5,5-dimethylpiperazin-2-o-
ne; N.sup.1-tert-octyl-3,3,5,5-tetramethyl-diazepin-2-one;
N1-tert-octyl-3,3-pentamethylene-5,5-hexamethylene-diazepin-2-one;
N.sup.1-tert-octyl-3,3-pentamethylene-5,5-dimethylpiperazin-2-one;
trans-1,2-cyclohexane-bis-(N.sup.1-5,5-dimethyl-3,3-pentamethylene-2-pipe-
razinone;
trans-1,2-cyclohexane-bis-(N.sup.1-3,3,5,5-dispiropentamethylene-
-2-piperazinone);
N.sup.1-isopropyl-1,4-diazadispiro-(3,3,5,5)pentamethylene-2-piperazinone-
;
N.sup.1-isopropyl-1,4-diazadispiro-3,3-pentamethylene-5,5-tetramethylene-
-2-piperazinone;
N.sup.1-isopropyl-5,5-dimethyl-3,3-pentamethylene-2-piperazinone;
trans-1,2-cyclohexane-bis-N.sup.1-(dimethyl-3,3-pentamethylene-2-piperazi-
none);
N.sup.1-octyl-5,5-dimethyl-3,3-pentamethylene-1,4-diazepin-2-one;
N.sup.1-octyl-1,4-diazadispiro-(3,3,5,5)pentamethylene-1,5-diazepin-2-one-
; or mixtures thereof.
[0275] Embodiment 21. A polymeric hollow article according to
embodiment 18, wherein the light stabilizer is an ultraviolet light
absorber chosen from a 2-hydroxybenzophenone, a
2-(2'-hydroxyphenyl)benzotriazole, a
2-(2'-hydroxyphenyl)-1,3,5-triazine, or mixtures thereof.
[0276] Embodiment 22. A polymeric hollow article according to
embodiment 21, wherein the ultraviolet light absorber is a
2-(2'-hydroxyphenyl)-1,3,5-triazine according to Formula (VII):
##STR00032##
wherein
[0277] each of R.sub.34 and R.sub.35 is independently chosen from
optionally substituted C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.10
hydrocarbyl-substituted amino, C.sub.1-C.sub.10 acyl or
C.sub.1-C.sub.10 alkoxyl; and
[0278] R.sub.36 is present at from 0 to 4 positions of the phenoxy
portion of Formula (VII) and in each instance is independently
chosen from hydroxyl, C.sub.1-C.sub.12 hydrocarbyl,
C.sub.1-C.sub.12 alkoxyl, C.sub.1-C.sub.12 alkoxyester, or
C.sub.1-C.sub.12 acyl.
[0279] Embodiment 23. A polymeric hollow article according to
embodiment 22, wherein the 2-(2'-hydroxyphenyl)-1,3,5-triazine is
chosen from
4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine
(CYASORB.RTM. 1164 available from Cytec Industries Inc.);
4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine;
2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;
2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazi-
ne;
2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dime-
thylphenyl)-s-triazine;
2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine-
;
2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazi-
ne; 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine;
2,4-bis(4-biphenylyl)-6-[2-hydroxy-4-[(octyloxycarbonyl)ethylideneoxy]phe-
nyl]-s-triazine;
2,4-bis(4-biphenylyl)-6-[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-s-triazine;
2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-h-
ydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine;
2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4(-3-benzyloxy-2-hydroxypropylox-
y)phenyl]-s-triazine;
2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triaz-
ine;
2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy-2-hydroxypropy-
loxy)-5-.alpha.-cumylphenyl]-s-triazine;
methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hy-
droxypropoxy)phenyl]-s-triazine}; methylene bridged dimer mixture
bridged in the 3:5', 5:5' and 3:3' positions in a 5:4:1 ratio;
2,4,6-tris(2-hydroxy-4-isooctyloxycarbonyliso-propylideneoxy-phenyl)-s-tr-
iazine;
2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-.alpha.-cumy-
lphenyl)-s-triazine;
2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyl-
oxy)phenyl]-s-triazine;
2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)-phenyl]-s-tria-
zine; mixture of
4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropox-
y)phenyl)-s-triazine and
4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-tridecyloxy-2-hydroxypropo-
xy)phenyl)-s-triazine (Tinuvin.RTM. 400 available from Ciba
Specialty Chemicals Corp.);
4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4(3-(2-ethylhexyloxy)-2-hydroxy-
propoxy)-phenyl)-s-triazine;
4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine; or mixtures
thereof.
[0280] Embodiment 24. A polymeric hollow article according to
embodiment 18, wherein the light stabilizer is a hindered amine
light stabilizer and an ultraviolet light absorber.
[0281] Embodiment 25. A polymeric hollow article according to any
of embodiments 1 to 24, wherein the stabilizer composition further
comprises at least one of:
[0282] (i) a hydroxylamine according to Formula (VIII):
##STR00033##
[0283] wherein
[0284] T.sub.1 is chosen from an optionally substituted
C.sub.1-C.sub.36 hydrocarbyl, C.sub.5-C.sub.12 cycloalkyl, or
C.sub.7-C.sub.9 aralkyl; and
[0285] T.sub.2 is chosen from hydrogen or T.sub.1; or
[0286] (ii) a tertiary amine oxide according to Formula (IX):
##STR00034##
[0287] wherein
[0288] each of W.sub.1 and W.sub.2 is independently a
C.sub.6-C.sub.36 hydrocarbyl chosen from straight or branched chain
C.sub.6-C.sub.36 alkyl, C.sub.6-C.sub.12 aryl, C.sub.7-C.sub.36
aralkyl, C.sub.7-C.sub.36 alkaryl, C.sub.6-C.sub.36 cycloalkyl,
C.sub.6-C.sub.36 alkcycloalkyl, or C.sub.6-C.sub.36
cycloalkylalkyl;
[0289] W.sub.3 is a C.sub.1-C.sub.36 hydrocarbyl is chosen from
straight or branched chain C.sub.1-C.sub.36 alkyl, C.sub.6-C.sub.12
aryl, C.sub.7-C.sub.36 aralkyl, C.sub.7-C.sub.36 alkylaryl,
C.sub.5-C.sub.36 cycloalkyl, C.sub.6-C.sub.36 alkylcycloalky, and
C.sub.6-C.sub.36 cycloalkylalkyl;
[0290] with the proviso that at least one of W.sub.1, W.sub.2 or
W.sub.3 contains a R carbon-hydrogen bond; and
[0291] wherein said alkyl, aralkyl, alkaryl, cycloalkyl,
alkcycloalkyl and cycloalkylalkyl groups of W.sub.1, W.sub.2 and
W.sub.3 may be interrupted by from one to sixteen groups chosen
from --O--, --S--, --SO--, --SO.sub.2--, --COO--, --OCO--, --CO--,
--NW.sub.4--, --CONW.sub.4-- or --NW.sub.4CO--, or wherein said
alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and
cycloalkylalkyl groups of W.sub.1, W.sub.2 and W.sub.3 are
substituted with from one to sixteen groups chosen from --OW.sub.4,
--SW.sub.4, --COOW.sub.4, --OCOW.sub.4, --COW.sub.4,
--N(W.sub.4).sub.2, --CON(W.sub.4).sub.2, --NW.sub.4COW.sub.4 and
5- and 6-membered rings containing the group
--C(CH.sub.3)(CH.sub.2R.sub.x)NL(CH.sub.2R.sub.x)(CH.sub.3)C--;
and
[0292] wherein
[0293] W.sub.4 is chosen from hydrogen or C.sub.1-C.sub.8
alkyl;
[0294] R.sub.x is chosen from hydrogen or methyl; and
[0295] L is chosen from C.sub.1-C.sub.30 alkyl, --C(O)R or --OR,
wherein R is C.sub.1-C.sub.30 straight or branched chain alkyl;
or
[0296] wherein said alkyl, aralkyl, alkaryl, cycloalkyl,
alkcycloalkyl and cycloalkylalkyl groups of W.sub.1, W.sub.2 and
W.sub.3 are both interrupted and substituted by any of the groups
mentioned above; or
[0297] wherein said aryl groups of W.sub.1, W.sub.2 and W.sub.3 are
substituted with from one to three substituents independently
chosen from halogen, C.sub.1-C.sub.8 alkyl or C.sub.1-C.sub.8
alkoxy; or
[0298] (iii) mixtures of (i) and (ii).
[0299] Embodiment 26. A polymeric hollow article according to
embodiment 25, wherein the hydroxylamine according to Formula
(VIII) is an N,N-dihydrocarbylhydroxylamine wherein each of T.sub.1
and T.sub.2 is independently chosen from benzyl, ethyl, octyl,
lauryl, dodecyl, tetradecyl, hexadecyl, heptadecyl or octadecyl; or
wherein each of T.sub.1 and T.sub.2 is the alkyl mixture found in
hydrogenated tallow amine.
[0300] Embodiment 27. A polymeric hollow article according to
embodiment 25 or 26, wherein the hydroxylamine according to Formula
(VIII) is an N,N-dihydrocarbylhydroxylamine chosen from
N,N-dibenzylhydroxylamine; N,N-diethylhydroxylamine;
N,N-dioctylhydroxylamine; N,N-dilaurylhydroxylamine;
N,N-didodecylhydroxylamine; N,N-ditetradecylhydroxylaamine;
N,N-dihexadecylhydroxylamine; N,N-dioctadecylhydroxylamine;
N-hexadecyl-N-tetradecylhydroxylamine;
N-hexadecyl-N-heptadecylhydroxylamine;
N-hexadecyl-N-octadecylhydroxylamine;
N-heptadecyl-N-octadecylhydroxylamine; N,N-di(hydrogenated
tallow)hydroxylamine; or mixtures thereof.
[0301] Embodiment 28. A polymeric hollow article according to any
of embodiments 1 to 27, wherein the hollow article further
comprises at least one co-additive chosen from nucleating agents,
fillers, reinforcing agents, polymer additives or mixtures
thereof.
[0302] Embodiment 29. A polymeric hollow article according to any
of embodiments 1 to 28, wherein the polyolefin is at least one of
linear low density polyethylene (LLDPE), medium density
polyethylene (MDPE), high density polyethylene (HDPE), or
polypropylene.
[0303] Embodiment 30. A polymeric hollow article according to any
of embodiments 1 to 29, wherein the basic co-additive (iii) is at
least one of calcium stearate, zinc stearate, magnesium behenate,
magnesium stearate, sodium ricinoleate or potassium palmitate.
[0304] Embodiment 31. A polymeric hollow article according to any
of embodiments 1 to 30, wherein the polyolefin, chroman-based
compound, phosphite or phosphonite, and at least one basic
co-additive, and amounts of the chroman-based compound, phosphite
or phosphonite, and at least one basic co-additive are selected so
that the polyolefin remains stable and retains its optimal
mechanical and/or physical properties over a longer period of time
in the oven, even in the absence of a sterically hindered amine
light stabilizer (HALS).
[0305] Embodiment 32. A polymeric hollow article according to any
of embodiments 1 to 31, wherein the polyolefin, chroman-based
compound, phosphite or phosphonite, and at least one basic
co-additive, and amounts of the chroman-based compound, phosphite
or phosphonite, and at least one basic co-additive are selected so
that at least one of the following results are obtained in a
rotational molding operation employed to produce the polymeric
hollow article, even in the absence of sterically hindered amine
light stabilizers (HALS):
[0306] a maximum mean failure energy (MFE) of the polymeric article
is reached at a shorter time interval;
[0307] a higher MFE of the polymeric article is retained over a
longer heating time; or
[0308] a processing window is enlarged to a peak internal air
temperature (PIAT) of up to 452.degree. F. with yellowness index of
the article remaining substantially unchanged up to a PIAT of
452.degree. F.
[0309] Embodiment 33. A polymeric hollow article according to
embodiment 31 or 32, wherein the results are obtained even in the
absence of antistatic agents.
[0310] Embodiment 34. A stabilizer composition for use in producing
a polymeric hollow article in a rotomolding process, the stabilizer
composition comprising a stabilizing amount of:
[0311] (i) at least one chroman-based compound according to Formula
(V):
##STR00035##
wherein
[0312] R.sub.21 is present at from 0 to 4 positions of the aromatic
portion of Formula (V) and in each instance is independently chosen
from: [0313] C.sub.1-C.sub.12 hydrocarbyl; [0314] NR'R'', wherein
each of R' and R'' is independently chosen from H or
C.sub.1-C.sub.12 hydrocarbyl; or [0315] OR.sub.27, wherein R.sub.27
is chosen from C.sub.1-C.sub.12 hydrocarbyl, COR''', or
Si(R.sub.28).sub.3, wherein R''' is chosen from H or
C.sub.1-C.sub.20 hydrocarbyl; and wherein R.sub.28 is chosen from
C.sub.1-C.sub.12 hydrocarbyl or alkoxy;
[0316] R.sub.22 is chosen from H or C.sub.1-C.sub.12
hydrocarbyl;
[0317] R.sub.23 is chosen from H or C.sub.1-C.sub.20
hydrocarbyl;
[0318] each of R.sub.24-R.sub.25 is independently chosen from H,
C.sub.1-C.sub.12 hydrocarbyl or OR'''',
wherein R'''' is chosen from H or C.sub.1-C.sub.12 hydrocarbyl;
and
[0319] R.sub.26 is H or a bond which together with R.sub.25 forms
.dbd.O;
[0320] (ii) at least one phosphite or phosphonite; and
[0321] (iii) a basic co-additive selected from alkali metal or
alkaline metal salts of higher fatty acids.
[0322] Additional embodiments of the individual elements of the
stabilizer composition (e.g., chroman-based compound, phosphite or
phosphonite, and basic co-additive) are substantially similar to
those contemplated above for the polymeric hollow article, but are
not repeated herewith.
EXAMPLES
[0323] The following examples are provided to assist one skilled in
the art to further understand certain embodiments of the present
disclosure. These examples are intended for illustration purposes
and are not to be construed as limiting the scope of the various
embodiments of the present disclosure.
Example 1--Preparation of Polyolefin Hollow Articles Using the
Rotational Molding Process
[0324] 50-lb. batches of LLDPE formulated with any type of
commercially available stabilizer additive package is dry blended
and compounded at 190.degree. C. on a Davis Standard single screw
extruder, with a 24:1 L/D screw with a mixing head running at 65
RPM. The resulting pellets are ground to rotomesh powder (less than
35 micron) on a Reduction Engineering pulverizor.
[0325] Using enough resin to produce a 1/8''-1/4'' thick walled
part, the formulation is rotationally molded using laboratory scale
equipment (e.g., a Ferry E-40 shuttle rotational molder). The
ground resin is placed in a cast aluminum mold, which is rotated
biaxially in a gas fired oven heated to a temperature of
630.degree. F. (332.degree. C.). The arm ratio for the cast
aluminum mold is 8:2. After rotating in the oven for specific time
intervals, the mold is removed from the oven and air cooled for 13
minutes while still rotating, followed by a 2 minute water spray,
and then 1 minute in circulating air. After the cooling cycle, the
mold is opened and the hollow part is removed and then tested by
measuring the mean failure energy (MFE) of the part. Sections can
be cut from the part and then tested according to the "Dart Drop
Low Temperature Impact Resistance Test Procedure," per American
Rotational Molders (ARM).
[0326] Formulations that achieve the highest mean fracture energy
(MFE) at the shortest rotational molding time interval are
desirable (reduced cycle time), as well as formulations that show
retention of high MFE at longer cycle times (broad process
window).
[0327] The color (or yellowness) of the molded part can also be
tested. Prior to the impact test, the impact specimen from the
upper left corner is read for color. The sample is read using a
GretagMacbeth Color i7 spectrophotometer. The yellowness according
to ASTM D1925 is reported from the mold side of the roto molded
part. Positive yellowness values indicates presence and magnitude
of yellowness (generally unfavorable), while a negative yellowness
value indicates that a material appears bluish (generally
favorable).
Example 2--Preparation of Polyolefin Hollow Articles Using the
Rotational Molding Process--(Comparative)
[0328] Control and test samples are prepared and tested according
to Example 1 above. The additive formulation for each sample is
provided in Table 1 below.
TABLE-US-00001 TABLE 1 Sample Additive Formulation Control (high
phenolic) 0.075 % CYANOX.RTM. 1790 (phenolic) 0.06 % IRGAFOS.RTM.
168 (phosphite) 0.035 % zinc stearate (co-stabilizer) Comparative 1
(invention) 0.0075 % CYANOX.RTM. 1790 (phenolic) 0.06 % IRGAFOSO
168 (phosphite) 0.05 % vitamin E (chroman-based compound) 0.035 %
zinc stearate (co-stabilizer) Comparative 2 (low phenolic) 0.0075 %
CYANOXO 1790 (phenolic) 0.06 % IRGAFOSO 168 (phosphite) 0.035 %
zinc stearate (co-stabilizer)
[0329] In all cases the LLDPE resin contains 0.035% by weight of
the total polymer composition of zinc stearate. The samples are
rotomolded and tested according to the ARM procedure as described
in Example 1. The stabilizer formulations of the present invention
provide superior and unexpected properties compared to the
state-of-the-art stabilizer formulations used in the rotomolding
process. The mean failure energy (MFE) of the sample containing the
stabilizer formulation according to the invention reached maximum
MFE sooner than either of the control sample containing the typical
commercial stabilizer system or the sample containing the low
phenolic stabilizer system, and also maintained a higher MFE for a
longer period of time than expected (FIG. 1). Accordingly, the
rotomolded LLDPE sample containing the stabilizer formulation
according to the invention gave superior performance over both the
control sample and the low phenolic sample.
Example 3--Preparation of Polyolefin Hollow Articles Using the
Rotational Molding Process--(Comparative--Resin 1)
[0330] Control and test samples are prepared and tested according
to Example 1 above. The LLDPE resin is the same as in Example 2
(Resin 1). The additive formulation for each sample is provided in
Table 2 below.
TABLE-US-00002 TABLE 2 Sample Additive Formulation Control 0.035 %
IRGANOX.RTM. 3114 (phenolic antioxidant) 0.11 % IRGAFOS.RTM. 168
(phosphite) 0.035 % zinc stearate (co-stabilizer) Example 0.06 %
IRGAFOS.RTM. 168 (phosphite) 0.05 % vitamin E acetate
(chroman-based compound) 0.035 % zinc stearate (co-stabilizer)
[0331] The samples are rotomolded and tested according to the ARM
procedure as described in Example 1, to 1/4'' thickness. The
stabilizer formulations of the present invention provide superior
and unexpected properties compared to the state-of-the-art
stabilizer formulations used in the rotomolding process. The mean
failure energy (MFE) of the sample containing the stabilizer
formulation according to the invention reached maximum MFE sooner
than the control sample containing the typical commercial
stabilizer system or the sample containing the low phenolic
stabilizer system, and also maintained a higher MFE for a longer
period of time than expected (FIG. 2A). Accordingly, the rotomolded
LLDPE sample containing the stabilizer formulation according to the
invention gave superior performance over both the control sample
and the low phenolic sample.
[0332] The Yellowness Index is also tested. As seen in FIG. 2B, the
Yellowness Index remains relatively flat in the rotomolded part
made with the stabilizer system according to the invention even as
the peak internal air temperature rises. Conversely, the Yellowness
Index rises as the peak internal air temperature rises in the
Control sample.
Example 4--Preparation of Polyolefin Hollow Articles Using the
Rotational Molding Process--(Comparative--Resin 2)
[0333] Control and test samples are prepared and tested according
to Example 1 above. However, in this Example the LLDPE resin (Resin
2) is provided by a different supplier than that of Examples 2 and
3. The additive formulation for each sample is provided in Table 3
below.
TABLE-US-00003 TABLE 3 Sample Additive Formulation Control 1 0.035
% IRGANOX.RTM. 3114 (phenolic antioxidant) 0.09 % IRGAFOS.RTM. 168
(phosphite) 0.035 % zinc stearate (co-stabilizer) Example 0.06 %
DOVERPHOS.RTM. 9228 (phosphite) 0.05 % vitamin E acetate
(chroman-based compound) 0.05 % zinc stearate (co-stabilizer)
Control 2 0.075 % CYANOX.RTM. 2777* (phenolic/phosphite) 0.35 zinc
stearate (co-stabilizer) * CYANOX.RTM. 2777 =CYANOX.RTM. 1790
(phenolic) + IRGAFOS.RTM. 168 (phosphite)
[0334] The samples are rotomolded and tested according to the ARM
procedure as described in Example 1, to 1/4'' thickness. Again, it
is seen that the stabilizer formulations of the present invention
provide superior and unexpected properties compared to the
state-of-the-art stabilizer formulations used in the rotomolding
process. The mean failure energy (MFE) of the sample containing the
stabilizer formulation according to the invention reached maximum
MFE sooner than either of the control sample containing the typical
commercial stabilizer system or the sample containing the low
phenolic stabilizer system, and also maintained a higher MFE for a
longer period of time than expected (FIG. 3A). Accordingly, the
rotomolded LLDPE sample containing the stabilizer formulation
according to the invention gave superior performance over both the
control samples.
[0335] The Yellowness Index is also tested. As seen in FIG. 3B, the
Yellowness Index remains lower as the peak internal air temperature
rises in the rotomolded part made with the stabilizer system
according to the invention than with either of the control
samples.
[0336] The results demonstrate that the heating times required to
achieve optimal cure of a polyolefin article using a standard
rotomolding process can be reduced by using the processing
stabilizer systems described in detail herein. Reduction of heating
times provides the direct benefits of lower energy costs and
increased production efficiency without compromising physical
and/or mechanical properties of the rotomolded article. The new
rotomolding processing stabilizer systems described herein are also
shown to provide a broad processing window, thereby enabling the
production of parts having high impact strength over a broader
range of peak internal air temperatures or heating times versus
conventional processing stabilizer systems. Accordingly, these new
processing stabilizer systems provide an excellent alternative to
other approaches and/or systems to accelerate the
sintering/densification of the polymer resin during the rotomolding
process.
[0337] Various patent and/or scientific literature references have
been referred to throughout this application. The disclosures of
these publications in their entireties are hereby incorporated by
reference as if written herein. In view of the above description
and the examples, one of ordinary skill in the art will be able to
practice the disclosure as claimed without undue
experimentation.
[0338] Although the foregoing description has shown, described, and
pointed out the fundamental novel features of the present
teachings, it will be understood that various omissions,
substitutions, and changes in the form of the detail of the
apparatus as illustrated, as well as the uses thereof, may be made
by those skilled in the art, without departing from the scope of
the present teachings. Consequently, the scope of the present
teachings should not be limited to the foregoing discussion, but
should be defined by the appended claims.
* * * * *