U.S. patent application number 12/743071 was filed with the patent office on 2010-10-21 for liquid stabilizer mixture.
This patent application is currently assigned to BASF SE. Invention is credited to Bernd Bruchmann, Jochen Fink, Simon Schambony.
Application Number | 20100267893 12/743071 |
Document ID | / |
Family ID | 40679049 |
Filed Date | 2010-10-21 |
United States Patent
Application |
20100267893 |
Kind Code |
A1 |
Schambony; Simon ; et
al. |
October 21, 2010 |
LIQUID STABILIZER MIXTURE
Abstract
A mixture comprising (a) one or more liquid UV absorbers, with
the proviso that Tinuvin 384-2 as a liquid UV absorber is excluded,
(b) one or more branched polymers comprising stabilizing groups,
(c) optionally one or more further additions. Use of such a mixture
for stabilizing inanimate organic materials against the effect of
light, oxygen and/or heat. Inanimate organic materials comprising
at least one such mixture, and also articles produced from such
inanimate organic materials. Methods of stabilizing inanimate
organic materials against the effect of light, oxygen and/or heat
by adding to said inanimate organic materials at least one such
mixture in an effective amount.
Inventors: |
Schambony; Simon;
(Ludwigshafen, DE) ; Fink; Jochen; (Nussloch,
DE) ; Bruchmann; Bernd; (Freinsheim, DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, L.L.P.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
BASF SE
Ludwigshafen
DE
|
Family ID: |
40679049 |
Appl. No.: |
12/743071 |
Filed: |
November 24, 2008 |
PCT Filed: |
November 24, 2008 |
PCT NO: |
PCT/EP2008/066050 |
371 Date: |
May 14, 2010 |
Current U.S.
Class: |
524/590 ;
252/589; 524/612; 558/406; 560/55 |
Current CPC
Class: |
C08K 5/315 20130101;
C08L 21/00 20130101; C08K 5/101 20130101; C08K 5/3492 20130101 |
Class at
Publication: |
524/590 ;
252/589; 524/612; 558/406; 560/55 |
International
Class: |
C08L 75/04 20060101
C08L075/04; F21V 9/06 20060101 F21V009/06; C08L 69/00 20060101
C08L069/00; C07C 255/00 20060101 C07C255/00; C07C 69/73 20060101
C07C069/73 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 28, 2007 |
EP |
07121782.2 |
Claims
1. A mixture comprising (a) one or more UV absorbers which are
liquid at a temperature of from 5 to 40.degree. C. and a pressure
of from 500 to 1500 mbar, with the proviso that the mixture of 95%
benzene propanoic acid
3-2(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-C.sub.7-9--
branched and linear alkyl esters and 5% 1-methoxy-2-propyl acetate
as a liquid UV absorber is excluded, (b) one or more branched
polymers comprising a stabilizing group, (c) optionally one or more
further additions.
2. The mixture according to claim 1, wherein the branched polymers
comprising a stabilizing group (b) are liquid at room
temperature.
3. The mixture according to claim 1, wherein the mixture is liquid
at room temperature.
4. The mixture according to claim 1, wherein the UV absorber (a) is
selected from the group consisting of cyanoacrylate, cinnamic
esters ester, benzotriazole, and triazine.
5. The mixture according to claim 4, wherein the UV absorber (a) is
2-ethylhexyl 2-cyano-3,3-diphenylacrylate or 2-ethylhexyl
4-methoxycinnamate.
6. The mixture according to claim 1, wherein the one or more
branched polymers comprising a stabilizing group comprise a
hyperbranched structure.
7. The mixture according to claim 1, wherein the branched polymer
comprises a carbonate group.
8. The mixture according to claim 1, wherein the branched polymer
comprises urethane, allophanate, urea and/or biuret groups.
9. The mixture according to claim 1, wherein the branched polymer
comprises a HALS group as a stabilizing group.
10. The mixture according to claim 1, further comprising as
optional component (c) an antioxidant, a flame retardant and/or a
colorant.
11-13. (canceled)
14. A plastic comprising at least one mixture according to claim
1.
15. An article produced from plastics according to claim 14.
16. A method of stabilizing plastic against the effect of light,
oxygen and/or heat, which comprises adding to said plastic at least
one mixture according to claim 1, in an effective amount.
Description
[0001] The invention relates to mixtures which comprise [0002] (a)
one or more liquid UV absorbers, with the proviso that Tinuvin
384-2 as a liquid UV absorber is excluded, [0003] (b) one or more
branched polymers comprising stabilizing groups, [0004] (c)
optionally one or more further additions.
[0005] The present invention additionally discloses methods of
stabilizing inanimate organic materials, more particularly
plastics, against the effect of light, oxygen and/or heat, using
this mixture. The invention further relates to articles produced
from inanimate organic materials thus stabilized.
[0006] Further embodiments of the present invention are evident
from the claims, the description, and the examples. It is
understood that the features of the inventive subject matter that
are specified above, and those still to be elucidated below, can be
used not only in the specific combination in which they are given
in each case, but also in other combinations as well, without
departing the scope of the invention. Preference, and very great
preference, respectively, is also given more particularly to those
embodiments of the present invention in which all of the features
of the inventive subject matter have the preferred and,
respectively, very preferred definitions.
[0007] Inanimate organic materials, more particularly plastics, are
known to be destroyed, often rapidly, by the action especially of
light, oxygen and/or heat. This destruction is typically manifested
in yellowing, discoloration, cracking or embrittlement of the
material. The aim of stabilizers, such as light stabilizers, for
example, is therefore to obtain satisfactory protection against the
destruction of inanimate organic material by light, oxygen and/or
heat.
[0008] Derivatives of 2,2,6,6-tetraalkylpiperidine have been
employed commercially for approximately three decades, under the
name HALS (Hindered Amine Light Stabilizers), as light stabilizers
and as stabilizers, more particularly for plastics and coating
materials.
[0009] It is also known to the skilled worker that mixtures of two
or more stabilizers, such as antioxidants, HALS compounds and/or UV
absorbers, for example, can be employed for the purpose of
stabilizing polymers.
[0010] EP 1 363 883 B1 discloses stabilizers which comprise HALS
compounds. They are used for stabilizing polymers. That
specification also describes compositions which among other
components may also comprise UV absorbers.
[0011] EP 1 060 225 B1 describes a process for preparing liquid
polyfunctional additives. These polyfunctional additives are used
for stabilizing organic material, polymers for example. Besides the
polyfunctional additives the stabilized materials may additionally
comprise further additives, such as UV absorbers, for example.
[0012] WO 02/092668 A1 describes additives which comprise known
polymer additives in the form of groups attached chemically to
hyperbranched or dendritic polymers or copolymers. These polymer
additives may be UV absorbers or else HALS compounds, for example.
That specification also discloses compositions comprising these
stabilizers. Furthermore, these compositions may also comprise
other conventional additives, such as UV absorbers or light
stabilizers, for example.
[0013] WO 2004/094505 A1 discloses stabilizers composed of highly
branched polymers having functional groups, as a highly branched
anchor group, and one or more stabilizing groups, which protect
plastics against damage due to heat, UV radiation, oxidation,
hydrolysis or mechanical exposure during processing, the
stabilizing groups being coupled to the anchor group via functional
groups which are able to react with the functional groups of the
highly branched polymers.
[0014] WO 2005/070987 A1 discloses stabilizers composed of one or
more polyisocyanates having on average 2 to 10 isocyanate groups
per molecule and, per mole of isocyanate groups, 0.1 to 1.0 mol of
one or more stabilizing groups, which protect plastics against
damage due to heat, UV radiation, oxidation, hydrolysis or
mechanical exposure during processing, the stabilizing groups being
coupled to the polyisocyanates via functional groups which are able
to react with the isocyanate groups. The stabilizing groups are
selected from phenols, sterically hindered amines (HALS compounds),
benzotriazoles, benzophenones, aromatic amines, and phosphites.
[0015] Our unpublished international application PCT/EP2007/057427
describes branched additives which can be used as stabilizers in
polymers. The branched additives of PCT/EP2007/057427 may comprise
HALS compounds and are used for stabilizing thermoplastics and
thermosets against, for example, oxidative, thermal or
radiation-induced degradation.
[0016] The stabilized thermoplastic molding compounds disclosed in
WO 2006/048206 A1 may comprise branched stabilizers having HALS
groups.
[0017] Although these compounds and mixtures are already
established in commercial practice, there nevertheless remains room
for improvements, more particularly in respect of the handling of
the stabilizers and the miscibility of the stabilizers with the
compounds that are to be stabilized. Oftentimes it is the case that
stabilizers or their mixtures are solid substances, which
frequently, in the form of powders, are not easy to meter. In
certain cases, furthermore, it is difficult to incorporate solid
stabilizers into the materials to be stabilized while achieving a
homogeneous distribution of the stabilizers. In these cases it is
frequently necessary to disperse or dissolve the stabilizers in a
solvent. That approach, however, entails additional worksteps.
Moreover, dissolved or dispersed stabilizers have lower
concentrations of effective compound and their transportation is
therefore unfavorable. Frequently moreover, liquid components are
already used in the preparation or processing of the material to be
stabilized (examples being polyols in the preparation of
polyurethanes, or plasticizers in the processing of plastics). In
this case, of course, the admixing of a liquid additive is
particularly beneficial.
[0018] It was an object of the present invention, therefore, to
provide mixtures which are easy to handle and easy to incorporate
into the materials to be stabilized. A further object of the
invention was to provide liquid stabilizer mixtures which can be
incorporated in liquid form into the materials to be stabilized, do
not have any tendency to migrate from the stabilized materials, and
at the same time exhibit a low volatility. A further sub-object of
the present invention was to provide mixtures, more particularly
liquid mixtures, which have a high stabilizer concentration and can
also be transported economically. A further object of the invention
was to provide mixtures which efficiently stabilize materials
against the effect of light, oxygen and/or heat.
[0019] Accordingly, the mixtures described at the outset have been
found.
[0020] For the purposes of this invention, expressions of the form
C.sub.a-C.sub.b identify chemical compounds or substituents having
a particular number of carbon atoms. The number of carbon atoms can
be selected from the entire range from a to b, including a and b; a
is at least 1 and b is always greater than a. The chemical
compounds or substituents are further particularized by expressions
of the form C.sub.a-C.sub.b V. V here is a chemical class of
compound or substituent, and represents alkyl compounds or alkyl
substituents, for example.
[0021] Halogen is fluorine, chlorine, bromine or iodine, preferably
fluorine, chlorine or bromine, more preferably fluorine or
chlorine.
[0022] Heteroatoms are preferably oxygen, nitrogen, sulfur or
phosphorus.
[0023] The various collective terms indicated have the following
particular definition unless otherwise indicated:
[0024] C.sub.1-C.sub.30 alkyl: straight-chain or branched
hydrocarbon radicals having up to 30 carbon atoms, examples being
C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.10 alkyl or C.sub.11-C.sub.20
alkyl, preferably C.sub.1-C.sub.10 alkyl, e.g., C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.3 alkyl, such as
methyl, ethyl, n-propyl, isopropyl, or C.sub.4-C.sub.6 alkyl,
n-butyl, sec-butyl, 1,1-dimethylethyl, pentyl, 2-methylbutyl,
1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl,
1-ethylpropyl, hexyl, 2-methylpentyl, 3-methyl-pentyl,
1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,
2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl,
2-ethylbutyl, 1,1,2-trimethyl-propyl, 1,2,2-trimethylpropyl,
1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, or C.sub.7-C.sub.10
alkyl, such as heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl,
1,1,3,3-tetramethylbutyl, nonyl or decyl (e.g., 2-propylheptyl),
and also their isomers.
[0025] C.sub.2-C.sub.22 alkenyl: unsaturated, straight-chain or
branched hydrocarbon radicals having 2 to 22 carbon atoms and at
least one double bond, preferably one double bond, in any desired
position, examples being C.sub.2-C.sub.10 alkenyl or
C.sub.11-C.sub.22 alkenyl, preferably C.sub.2-C.sub.10 alkenyl such
as C.sub.2-C.sub.4 alkenyl, such as ethenyl, 1-propenyl,
2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl,
1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl,
2-methyl-2-propenyl, or C.sub.5-C.sub.6 alkenyl, such as
1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl,
2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl,
2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl,
2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl,
1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl,
1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl,
3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl,
2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl,
1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl,
4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl,
3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl,
2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,
1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,
1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,
1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl,
1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,
2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,
2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,
3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl,
1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl,
2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,
1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl or
1-ethyl-2-methyl-2-propenyl, and also C.sub.7-C.sub.10 alkenyl,
such as the isomers of heptenyl, octenyl, nonenyl or decenyl.
[0026] C.sub.3-C.sub.15 cycloalkyl: monocyclic, saturated
hydrocarbon groups having 3 up to 15 carbon ring members,
preferably C.sub.3-C.sub.8 cycloalkyl such as cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, and
also a saturated or unsaturated polycyclic system such as norbornyl
or norbenzyl, for example. Particular preference is given to
C.sub.5-C.sub.6 cycloalkyl.
[0027] Aryl: mono- to tricyclic aromatic ring system comprising 6
to 14 carbon ring members, e.g., phenyl, hydroxyphenyl, naphthyl or
anthracenyl, preferably a mono- to dicyclic, more preferably a
monocyclic aromatic ring system.
[0028] Heterocycles: five- to twelve-membered, preferably five- to
nine-membered, more preferably five- to six-membered ring systems
containing oxygen, nitrogen and/or sulfur atoms, if appropriate
containing two or more rings, such as furyl, thiophenyl, pyrryl,
pyridyl, imidazolyl, indolyl, benzoxazolyl, dioxolyl, dioxyl,
benzimidazolyl, benzo-thiazolyl, dimethylpyridyl, methylquinolyl,
dimethylpyrryl, methoxyfuryl, dimethoxy-pyridyl, difluoropyridyl,
methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
[0029] C.sub.1-C.sub.20 alkoxy is a straight-chain or branched
alkyl group having 1 to 20 carbon atoms (as specified above) which
are attached via an oxygen atom (--O--), examples being
C.sub.1-C.sub.10 alkoxy such as n-hexoxy, isohexoxy, n-octoxy,
2-ethylhexoxy, and isooctoxy, and additionally also methoxy,
ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy,
tert-butoxy, n-pentoxy, n-nonoxy, n-decoxy, or C.sub.11-C.sub.20
alkoxy such as n-undecoxy and n-dodecoxy, preferably
C.sub.1-C.sub.10 alkyloxy, more preferably C.sub.1-C.sub.8 alkoxy,
such as methoxy, ethoxy, propoxy or octoxy, for example.
[0030] C.sub.1-C.sub.22 alkylene: straight-chain or branched
hydrocarbon radicals having 1 to 22 carbon atoms, examples being
C.sub.2-C.sub.10 alkylene or C.sub.11-C.sub.22 alkylene, preferably
C.sub.2-C.sub.10 alkylene, more particularly methylene,
dimethylene, trimethylene, tetramethylene, penta-methylene or
hexamethylene.
[0031] Substances that are "liquid" are substances, in the context
of the present application, which at temperatures of 5 to
40.degree. C. and a pressure of 500 to 1500 mbar present as good as
no resistance to dimensional change but present extremely great
resistance to a volume change. A further feature of the liquid
substances is that they have a dynamic viscosity in the range from
1 to 150 000 mPas, preferably to 10 000 mPas, determined at
23.degree. C. and 1 bar, in accordance for example with DIN
53019.
[0032] By "dendrimeric" is meant, in the context of the present
invention, that the degree of branching (DB) is 99.9%-100%. On the
definition of the degree of branching see H. Frey et al., Acta
Polym. 1997, 48, 30.
[0033] "Hyperbranched polymers" are molecularly and structurally
nonuniform. They differ from linear polymers in that they comprise
side groups which are composed of the same monomers as the polymer
backbone. They further differ, for example, in their molecular
nonuniformity from dendrimers, and are considerably easier to
prepare. By "hyperbranched" is also meant, in the context of the
present invention, that the degree of branching is 10% to 99.9%,
preferably 20% to 99%, more preferably 20% to 95%.
[0034] The degree of branching (DB) is defined as
DB = T + Z T + Z + L .times. 100 % , ##EQU00001##
where T is the average number of terminally bonded monomer units, Z
is the average number of monomer units which form branches, and L
is the average number of linearly bonded monomer units in the
macromolecules of the compounds in question.
[0035] "Branched polyisocyanates" for the purposes of this
invention are oligomeric and polymeric isocyanates which comprise
groups formed by the reaction of polyvalent isocyanates. The groups
in question are, for example, urethane, allophanate, urea, biuret,
uretdione, amide, isocyanurate, carbodiimide, uretonimine,
oxadiazinetrione or iminooxadiazinedione groups, which in some
cases lead to branching. The branched polyisocyanates can therefore
be characterized as oligomeric or polymeric compounds (dimers,
trimers, tetramers or higher multimers) of the polyvalent
isocyanates.
[0036] "Hyperbranched polycarbonates" for the purposes of this
invention are noncrosslinked macromolecules with hydroxyl and
carbonate or carbamoyl chloride groups which are both structurally
and molecularly nonuniform. In one version of the present invention
they may have a composition, starting from a central molecule,
analogous with that of dendrimers, but with a nonuniform branch
chain length. In another version of the present invention they may
be of linear composition, with functional side groups, or else may,
as a combination of the two extremes, have linear and branched
moieties. On the definition of dendrimeric and hyperbranched
polymers see also P. J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and
H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499.
[0037] "Branched polymers" may for example be branched
polyisocyanates or hyperbranched polycarbonates.
[0038] "Stabilizing additives" are known. Their function is to
protect compounds against the adverse influence of detrimental
environmental effects, caused for example by light, oxygen and/or
heat. Examples of such stabilizing additives include antioxidants,
hydrolysis inhibitors, quenchers, flame retardants or light
stabilizers.
[0039] "Stabilizing groups" are frequently based on stabilizing
additives. These are the part or parts of the stabilizing additive
whose effect on interaction with light, heat, oxygen, peroxides,
free radicals and/or other damaging molecules or conditions is to
prevent or at least reduce the damage. The stabilizing groups are
attached covalently to the branched polymers. Preferably the
stabilizing groups are attached covalently to the chain ends of the
branched polymers. In principle a branched polymer may comprise one
or more stabilizing groups, including different stabilizing groups.
The number and the proportion of the stabilizing groups to one
another are variable and are limited only by the number of
attachment points in the branched polymer (covalent bonds) to the
stabilizing groups. In this context, however, it is not necessary
for every attachment point to have been reacted with a stabilizing
group. Where a branched polymer comprising stabilizing groups (b)
is to act, for example, as an antioxidant, that polymer may
comprise those stabilizing groups which retard or arrest the
oxidative degradation of a plastic.
[0040] In the mixtures of the invention, component (a) comprises
one or more different liquid UV absorbers.
[0041] Liquid UV absorbers are frequently commercial products. They
are sold, for example, under the trade name Uvinul.RTM. by BASF
Aktiengesellschaft, Ludwigshafen. The Uvinul.RTM. light stabilizers
comprise compounds of the following classes: benzophenones,
benzotriazoles, cyanoacrylates, cinnamic esters,
para-aminobenzoates, and naphthalimides. Furthermore, other known
chromophores are used, examples being hydroxyphenyltriazines or
oxalanilides. Compounds of this kind are used, for example, alone
or in mixtures with other light stabilizers in cosmetic
applications, sun protection products for example, or for
stabilizing organic polymers. Preferred liquid UV absorbers are
cyanoacrylates, cinnamic esters, benzotriazoles or triazines.
Liquid UV absorbers used with particular preference are
2-ethylhexyl 2-cyano-3,3-diphenyl acrylate or 2-ethylhexyl
4-methoxycinnamate. A liquid UV absorber used with very particular
preference is 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. A further
liquid UV absorber used with very particular preference is
2-ethylhexyl 4-methoxycinnamate.
[0042] Further examples of liquid UV absorbers are as follows:
2-ethylhexyl N,N-dimethyl-4-aminobenzoate,
3,3,5-trimethylcyclohexyl salicylate, 2-ethylhexyl salicylate,
isoamyl 4-methoxycinnamate,
2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol,
3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenylpropanoic
acid C.sub.7-9 alkyl esters,
.beta.-[3-(2H-benzotriazol-2-yl)-4-hydroxy-5-tert-butylphenyl]propanoic
acid poly(ethylene glycol) 300 ester,
bis{(.beta.-[3-(2H-benzotriazol-2-yl)-4-hydroxy-5-tert-butylphenyl]propan-
oic acid} poly(ethylene glycol) 300 ester.
[0043] Further suitable liquid UV absorbers are evident from the
text of Cosmetic Legislation, Vol. 1, Cosmetic Products, European
Commission 1999, pp. 64-66, hereby expressly incorporated by
reference.
[0044] Suitable liquid UV absorbers are also described in lines 14
to 30 ([0030]) on page 6 of EP 1 191 041 A2. The skilled worker
knows which of these UV absorbers are liquid. This literature
reference is hereby incorporated to become part of the disclosure
content of the present invention.
[0045] The liquid UV absorbers do not comprise Tinuvin 384-2 (95%
benzenepropanoic acid,
3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-,
C7-9-branched and linear alkyl esters; 5% 1-methoxy-2-propyl
acetate), a UV absorber from Ciba Speciality Chemicals Inc.
[0046] Furthermore, in the mixtures of the invention, component (b)
is composed of one or more different branched polymers comprising
stabilizing groups.
[0047] In one preferred embodiment of the mixture of the invention
the branched polymers comprising stabilizing groups (b), or
mixtures thereof, are liquid.
[0048] Branched polymers comprising stabilizing groups (b) are
disclosed, for example, as "branched polymeric stabilizers" in WO
2004/094505 A1 (p. 4, I. 12-I. 26). The stabilizers disclosed there
are hereby expressly incorporated by reference.
[0049] The structure of the branched polymers comprising
stabilizing groups (b) is preferably hyperbranched.
[0050] Branched polymers comprising stabilizing groups (b) can be
prepared, for example, by the general processes described in WO
2004/094505 A1 (p. 8, I. 71-p. 13, I. 33). The preparation
processes disclosed therein are expressly incorporated by
reference.
[0051] With regard to the branched polymers comprising stabilizing
groups (b) and their preparation, including more particularly the
stabilizing groups described therein (active substance groups, p.
14, I. 1-p. 22, I. 4), the full content of WO 2004/094505 A1 is
incorporated by reference. Stabilizing compounds on which the
stabilizing groups are based are available commercially or are
obtainable from commercially available compounds by means of simple
reactions known to the skilled worker.
[0052] The mixtures of the invention preferably feature branched
polymers comprising stabilizing groups, as component (b), having a
number-average molecular weight, Mn, of 100 to 20 000 g/mol,
preferably 100-15 000 g/mol, more preferably 100-10 000 g/mol, and
very preferably 200-5000 g/mol.
[0053] Preferably the mixture of the invention comprises as
component (b) branched polymers comprising HALS compounds as
stabilizing groups.
[0054] In one preferred embodiment of the mixtures of the invention
the branched polymers comprising stabilizing groups (b) comprise
carbonate groups. In this case the polymers are preferably
hyperbranched.
[0055] The preparation of the hyperbranched polymers comprising
carbonate groups and stabilizing groups (b) can take place by the
methods indicated in our international application
PCT/EP2007/057427.
[0056] In accordance with the specification indicated above,
hyperbranched polycarbonates (i.e., hyperbranched polymers
comprising carbonate groups) with stabilizing groups can be
obtained by reacting [0057] (A) at least one compound having at
least three alcoholic hydroxyl groups, also referred to below as
compound (A) or, in accordance with the number of alcoholic
hydroxyl groups, triol (A) or tetrol (A) or pentol (A), for
example, with [0058] (B) at least one reagent of the formula I,
also referred to below as reagent (B),
[0058] ##STR00001## [0059] (C) and at least one reagent of the
general formula X.sup.3-(A.sup.1).sub.m-X.sup.4, also referred to
below as reagent (C), the variables being defined as follows:
[0060] X.sup.1 and X.sup.2 are alike or different and are selected
from halogen, bromine for example and chlorine more particularly,
C.sub.1-C.sub.20 alkoxy, preferably C.sub.1-C.sub.6 alkoxy groups
such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy
and isohexoxy, more preferably methoxy, ethoxy, n-butoxy, and
tert-butoxy; aryloxy, more particularly phenoxy, 1-naphthoxy,
2-naphthoxy or C.sub.1-C.sub.4 alkyl-substituted C.sub.6-C.sub.10
aryloxy, more particularly o-tolyloxy or p-tolyloxy, and
O--C(.dbd.O)-halogen, more particularly O--C(.dbd.O)--Cl; or
X.sup.1 and X.sup.2 together are a group of the formula O-Q-O,
where Q describes an unsubstituted or substituted
.alpha.,.omega.-alkylene group, more particularly ethylene.
[0061] Particularly preferred reagents (B) are phosgene, ethyl
chloroformate, diphosgene and triphosgene, and also dialkyl
carbonates or diaryl carbonates, examples being dimethyl carbonate,
diethyl carbonate, dibutyl carbonate (di-n-butyl carbonate,
di-tert-butyl carbonate), di-tert-butyl dicarbonate, di-tert-butyl
tricarbonate, diphenyl carbonate, ditolyl carbonate, diethylene
carbonate, ethylene carbonate, and propylene carbonate. Very
particular preference is given to dimethyl carbonate, diethyl
carbonate, dibutyl carbonate, ethylene carbonate, and propylene
carbonate.
[0062] Compound (A) is selected from compounds having at least
three alcoholic hydroxyl groups, examples being triols (A), tetrols
(A) or pentols (A).
[0063] Examples of suitable triols (A) are aliphatic, aromatic, and
benzylic triols, which may be unalkoxylated or alkoxylated one to
100 times per hydroxyl group, preferably alkoxylated with
C.sub.2-C.sub.4 alkylene oxide, such as ethylene oxide, propylene
oxide or 1,2-butylene oxide or mixtures of ethylene oxide and
propylene oxide and/or butylene oxide, for example, and more
particularly alkoxylated with ethylene oxide or propylene
oxide.
[0064] Mention may be made, by way of example, of the following:
glycerol, trimethylol-methane, 1,1,1-trimethylolethane,
1,1,1-trimethylolpropane, 1,2,4-butanetriol,
tris(hydroxymethyl)amine, tris(hydroxyethyl)amine,
tris(hydroxypropyl)amine, tris(hydroxymethyl) isocyanurate,
tris(hydroxyethyl) isocyanurate, phloroglucinol, trihydroxytoluene,
trihydroxydimethylbenzene, phloroglucides,
1,3,5-benzene-trimethanol, 1,1,1-tris(4'-hydroxyphenyl)methane,
1,1,1-tris(4'-hydroxyphenyl)ethane, trifunctional or higher
polyfunctional polyetherols based on trifunctional or higher
polyfunctional alcohols and ethylene oxide, propylene oxide or
butylene oxide, or polyesterols. Particular preference here is
given to glycerol, 1,1,1-trimethylolpropane, and their polyetherols
based on ethylene oxide or propylene oxide.
[0065] Preferred examples include glycerol and
(HO--CH.sub.2).sub.3C--X.sup.7, unalkoxylated or alkoxylated one to
a hundred times per hydroxyl group with C.sub.2-C.sub.4 alkylene
oxide, X.sup.7 being selected from a nitrogen atom and C--R.sup.6,
and R.sup.6 being selected from hydrogen and C.sub.1-C.sub.4 alkyl,
such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
sec-butyl, and tert-butyl. Very particular preference is given to
glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol,
singly to vigintuply alkoxylated glycerol, and singly to vigintuply
alkoxylated 1,1,1-trimethylolpropane (R.sup.6.dbd.C.sub.2H.sub.5),
the alkoxylating agents used being preferably ethylene oxide or
propylene oxide or mixtures thereof.
[0066] Examples of suitable tetrols (A) are pentaerythritol,
bis(trimethylolpropane), and diglycerol, which may be unalkoxylated
or alkoxylated one to 100 times per hydroxyl group, preferably
alkoxylated with C.sub.2-C.sub.4 alkylene oxide, such as ethylene
oxide, propylene oxide or 1,2-butylene oxide, or mixtures of
ethylene oxide and propylene oxide and/or butylene oxide, for
example, and more particularly alkoxylated with ethylene oxide or
propylene oxide.
[0067] Examples of suitable pentols (A) also comprise compounds
having more than 5 alcoholic hydroxyl groups per molecule. These
include triglycerol, polyglycerols, hexahydroxybenzene, or sugars,
such as sorbose, mannose or glucose, for example, more particularly
reduced sugars such as sorbitol, for example, which may be
unalkoxylated or alkoxylated one to 100 times per hydroxyl group,
preferably alkoxylated with C.sub.2-C.sub.4 alkylene oxide, such as
ethylene oxide, propylene oxide or 1,2-butylene oxide or mixtures
of ethylene oxide and propylene oxide and/or butylene oxide, for
example, and more particularly alkoxylated with ethylene oxide or
propylene oxide.
[0068] The compound (A) is preferably a trihydric or tetrahydric
alcohol, specifically glycerol, TMP
(1,1,1-tri(hydroxymethyl)propane, trimethylolpropane, CAS# 77-99-6)
or pentaerythritol which has been randomly etherified with from 1
to 5 mol of ethylene oxide, propylene oxide, butylene oxide or
mixtures thereof per mole of hydroxyl groups of the trihydric or
tetrahydric alcohol.
[0069] Furthermore, reaction is carried out with at least one
reagent of the general formula X.sup.3-(A.sup.1).sub.m--X.sup.4,
also referred to in the context of the present invention as reagent
(C), where [0070] X.sup.3 is a functional group selected from OH,
SH, NH.sub.2, NH--C.sub.1-C.sub.4 alkyl, where C.sub.1-C.sub.4
alkyl has been selected from methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, and tert-butyl, such as NH--CH.sub.3,
NH--C.sub.2H.sub.5, NH-n-C.sub.3H.sub.7, NH-iso-C.sub.3H.sub.7,
NH-n-C.sub.4H.sub.9, NH-iso-C.sub.4H.sub.9, NH-sec-C.sub.4H.sub.9,
NH-tert-C.sub.4H.sub.9, and also isocyanate, epoxy, examples
being
[0070] ##STR00002## COOH, COOR.sup.12, C(.dbd.O)--O--C(.dbd.O),
C(.dbd.O)--Cl, preferably COOH, COOR.sup.12, OH, and NH.sub.2,
[0071] R.sup.12 is C.sub.1-C.sub.4 alkyl or C.sub.6-C.sub.10 aryl
[0072] A.sup.1 is a single bond or a spacer, examples of spacers
A.sup.1 being para-phenylene, meta-phenylene, preferably
C.sub.2-C.sub.100 alkylene, preferably C.sub.2-C.sub.50 alkylene,
more preferably up to C.sub.20 alkylene, branched or unbranched,
and from one to 6 non-adjacent CH.sub.2 groups here can, if
appropriate, also have been replaced by, respectively, a sulfur
atom, which can also have been oxidized, or by an oxygen atom. The
following spacers may be mentioned by way of example: --CH.sub.2--,
--CH.sub.2--CH.sub.2--, --(CH.sub.2).sub.3--, --(CH.sub.2).sub.4--,
--(CH.sub.2).sub.5--, --(CH.sub.2).sub.6--, --(CH.sub.2).sub.7--,
--(CH.sub.2).sub.8--, --(CH.sub.2).sub.9--, --(CH.sub.2).sub.10--,
--(CH.sub.2).sub.12--, --(CH.sub.2).sub.14--,
--(CH.sub.2).sub.16--, --(CH.sub.2).sub.18--,
--(CH.sub.2).sub.20--, --CH.sub.2--CH(CH.sub.3)--,
--CH.sub.2--CH(C.sub.2H.sub.5)--,
--CH.sub.2--CH(CH[CH.sub.3].sub.2)--,
--CH.sub.2--CH(n-C.sub.3H.sub.7)--, --[CH(CH.sub.3)].sub.2--,
--CH(CH.sub.3)--CH.sub.2--CH.sub.2--CH(CH.sub.3)--,
--CH(CH.sub.3)--CH.sub.2--CH(CH.sub.3)--,
--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--,
--CH.sub.2--CH(n-C.sub.4H.sub.9)--,
--CH.sub.2--CH(iso-C.sub.3H.sub.7)--,
--CH.sub.2--CH(tert-C.sub.4H.sub.9)--, [0073] --CH.sub.2--O--,
--CH.sub.2--O--CH.sub.2--,
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--,
--[(CH.sub.2).sub.2--O].sub.2--(CH.sub.2).sub.2--,
--[(CH.sub.2).sub.2--O].sub.3--(CH.sub.2).sub.2--, [0074]
--CH.sub.2--S--, --CH.sub.2--S--CH.sub.2--,
--(CH.sub.2).sub.2--S--(CH.sub.2).sub.2--,
--[(CH.sub.2).sub.2--S].sub.2--(CH.sub.2).sub.2--,
--[(CH.sub.2).sub.2--S].sub.3--(CH.sub.2).sub.2--,
--CH.sub.2--SO--CH.sub.2--, --CH.sub.2--SO.sub.2--CH.sub.2--,
[0075] very particularly preferred spacers being C.sub.1-C.sub.10
alkylene groups, branched or unbranched, such as --CH.sub.2--,
--CH.sub.2--CH.sub.2--, --(CH.sub.2).sub.3--, --(CH.sub.2).sub.4--,
--(CH.sub.2).sub.6--, --(CH.sub.2).sub.6--, --(CH.sub.2).sub.7--,
--(CH.sub.2).sub.8--, --(CH.sub.2).sub.9--, --(CH.sub.2).sub.10--,
[0076] m is zero or one, [0077] X.sup.4 is a group selected from
phenol groups, benzophenones, aromatic amines, and
nitrogen-comprising heterocycles, in each case substituted or
unsubstituted; preferably a group selected from nitrogen-comprising
heterocycles, more particularly HALS groups.
[0078] X.sup.4 here assumes the role of the stabilizing group. The
reagents (C) are to a very large extent available commercially
(e.g., 2,2,6,6-tetramethylpiperidinol or
1,2,2,6,6-penta-methylpiperidinol) or are obtainable from these
commercially available compounds by standard methods of organic
synthesis.
[0079] Particular examples of phenol groups are sterically hindered
phenol groups, for example phenol groups substituted by one or two
isopropyl groups or tert-butyl groups in the ortho position
relative to the phenolic OH group. Particularly preferred examples
of phenol groups are
##STR00003##
[0080] A very particularly preferred example of a phenol group is
the 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid group.
[0081] Particular examples of benzophenone groups are
##STR00004##
[0082] Examples of aromatic amines are
##STR00005##
the variables being defined as follows: [0083] R.sup.6 has been
selected from hydrogen, [0084] C.sub.1-C.sub.12 alkyl, such as
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl,
1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl,
n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; [0085] more
preferably C.sub.1-C.sub.4 alkyl, such as methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, [0086]
C.sub.3-C.sub.12 cycloalkyl, such as cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,
cyclodecyl, cycloundecyl, and cyclododecyl; preferably cyclopentyl,
cyclohexyl, and cycloheptyl, [0087] C.sub.6-C.sub.14 aryl, for
example 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl,
9-anthracenyl and in particular phenyl, benzyl. [0088] R.sup.7 has
been selected from hydrogen, [0089] C.sub.1-C.sub.4 alkyl, methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and
tert-butyl.
[0090] Nitrogen-comprising heterocycles can be aromatic,
monounsaturated or saturated. Nitrogen-comprising heterocycles can
comprise one, two or three nitrogen atoms and can bear one or more
substituents; in the case of aromatic heterocycles, preference is
given to one or more hydroxyphenyl substituents.
[0091] Examples of aromatic heterocycles are benzotriazoles and
triazines, in particular those of the formulae
##STR00006##
which may each bear one or more further substituents, for example
hydroxyl or C.sub.1-C.sub.4 alkyl, in particular tert-butyl, also
C(CH.sub.3).sub.2(C.sub.6H.sub.5) or C(CH.sub.3).sub.2OH or
perfluoro-C.sub.1-C.sub.4 alkyl, in particular CF.sub.3 or
n-C.sub.4F.sub.9. Specific examples of nitrogen-comprising aromatic
heterocycles having one or more substituents are
##STR00007##
[0092] Particular examples of saturated nitrogen-comprising
heterocycles are the substituents which are known as HALS (hindered
amine light stabilizers) and have the formula II a or the formula
II b.
##STR00008##
the variables being defined as follows: [0093] R.sup.1, R.sup.2,
R.sup.3, and R.sup.4 are identical or different and are,
independently of one another, C.sub.1-C.sub.12 alkyl such as
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl,
1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl,
n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; more preferably
C.sub.1-C.sub.4 alkyl such as methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl or tert-butyl, and in particular each
of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is identical and is
methyl, [0094] C.sub.3-C.sub.12 cycloalkyl, such as cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,
cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl; preferably
cyclopentyl, cyclohexyl, and cycloheptyl, or in each case R.sup.1
and R.sup.2 and/or R.sup.3 and R.sup.4, together with the carbon
atom to which they are jointly attached, form a 4- to 8-membered
ring, [0095] X.sup.5 is an oxygen atom, a sulfur atom, an NH group,
an N--(C.sub.1-C.sub.4 alkyl) group, a carbonyl group, [0096]
preferably an oxygen atom, [0097] A.sup.2 is a single bond or a
spacer. Examples of spacers A.sup.2 are para-phenylene,
meta-phenylene, preferably C.sub.1-C.sub.20 alkylene, branched or
unbranched, where in each case one to 6 nonadjacent CH.sub.2 groups
can if appropriate be replaced by a sulfur atom, including oxidized
forms, or an oxygen atom. Mention may be made by way of example of
the following spacers: [0098] --CH.sub.2--, --CH.sub.2--CH.sub.2--,
--(CH.sub.2).sub.3--, --(CH.sub.2).sub.4--, --(CH.sub.2).sub.5--,
--(CH.sub.2).sub.6--, --(CH.sub.2).sub.7--, --(CH.sub.2).sub.8--,
--(CH.sub.2).sub.9--, --(CH.sub.2).sub.10--, --(CH.sub.2).sub.12--,
--(CH.sub.2).sub.14--, --(CH.sub.2).sub.16--,
--(CH.sub.2).sub.18--, --(CH.sub.2).sub.20--,
--CH.sub.2--CH(CH.sub.3)--, --CH.sub.2--CH(C.sub.2H.sub.5)--,
--CH.sub.2--CH(CH[CH.sub.3].sub.2)--,
--CH.sub.2--CH(n-C.sub.3H.sub.7)--, --[CH(CH.sub.3)].sub.2--,
--CH(CH.sub.3)--CH.sub.2--CH.sub.2--CH(CH.sub.3)--,
--CH(CH.sub.3)--CH.sub.2--CH(CH.sub.3)--,
--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--,
--CH.sub.2--CH(n-C.sub.4H.sub.9)--,
--CH.sub.2--CH(iso-C.sub.3H.sub.7)--,
--CH.sub.2--CH(tert-C.sub.4H.sub.9)--, [0099] --CH.sub.2--O--,
--CH.sub.2--O--CH.sub.2--,
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--,
--[(CH.sub.2).sub.2--O].sub.2--(CH.sub.2).sub.2--,
--[(CH.sub.2).sub.2--O].sub.3--(CH.sub.2).sub.2--, --CH.sub.2--S--,
--CH.sub.2--S--CH.sub.2--,
--(CH.sub.2).sub.2--S--(CH.sub.2).sub.2--,
--[(CH.sub.2).sub.2--S].sub.2--(CH.sub.2).sub.2--,
--[(CH.sub.2).sub.2--S].sub.3--(CH.sub.2).sub.2--,
--CH.sub.2--SO--CH.sub.2--, --CH.sub.2--SO.sub.2--CH.sub.2--,
[0100] preferred spacers A.sup.2 being C.sub.2-C.sub.10 alkylene
groups, branched or unbranched, such as --CH.sub.2--OH.sub.2--,
--(CH.sub.2).sub.3--, --(CH.sub.2).sub.4--, --(CH.sub.2).sub.5--,
--(CH.sub.2).sub.6--, --(CH.sub.2).sub.7--, --(CH.sub.2).sub.8--,
--(CH.sub.2).sub.9--, --(CH.sub.2).sub.10--; [0101] preferably
A.sup.2 is a single bond, [0102] n is zero or one, [0103] X.sup.6
is hydrogen, oxygen, [0104] O--C.sub.1-C.sub.19 alkyl, preferably
C.sub.1-C.sub.6 alkoxy groups such as methoxy, ethoxy, n-propoxy,
isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy,
n-pentoxy, isopentoxy, n-hexoxy, and isohexoxy, more preferably
methoxy or ethoxy, [0105] C.sub.1-C.sub.12 alkyl, preferably
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl,
1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl,
n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; more preferably
C.sub.1-C.sub.4 alkyl such as methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, and tert-butyl, [0106]
C.sub.2-C.sub.18 acyl, for example acetyl, propionyl, butyryl,
benzoyl, stearyl, [0107] or aryloxycarbonyl having 7 to 12 C atoms,
for example C.sub.6H.sub.5--OCO.
[0108] Examples of particularly well-suited HALS compounds
(stabilizing additives) on which the abovementioned stabilizing
compounds of the formula IIa or IIb may be based are [0109]
4-amino-2,2,6,6-tetramethylpiperidine, [0110]
4-amino-1,2,2,6,6-pentamethylpiperidine, [0111]
4-hydroxy-2,2,6,6-tetramethylpiperidine, [0112]
4-hydroxy-1,2,2,6,6-pentamethylpiperidine, [0113]
4-butylamino-2,2,6,6-tetramethylpiperidine, [0114]
4-butylamino-1,2,2,6,6-pentamethylpiperidine, [0115]
4-amino-2,2,6,6-tetramethylpiperidine-N-oxyl, [0116]
4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, [0117]
4-butylamino-2,2,6,6-tetramethylpiperidine-N-oxyl, [0118]
4-hydroxy-2,2,6,6-tetramethyl-1-octoxypiperidine, [0119]
4-amino-2,2,6,6-tetramethyl-1-octoxypiperidine, [0120]
4-butylamino-2,2,6,6-tetramethyl-1-octoxypiperidine
[0121] Very particularly suitable are
4-amino-2,2,6,6-tetramethylpiperidine,
4-amino-1,2,2,6,6-pentamethylpiperidine,
4-hydroxy-2,2,6,6-tetramethylpiperidine,
4-hydroxy-1,2,2,6,6-pentamethylpiperidine,
4-amino-2,2,6,6-tetramethylpiperidine-N-oxyl, and
4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl.
[0122] In one preferred embodiment of the mixture of the invention
the hyperbranched polycarbonate comprising HALS compounds is
obtained by reacting a mixture comprising: [0123] (A) one or more
polyhydric alcohols, [0124] (B) one or more carbonates, [0125] (C)
one or more HALS compounds comprising a functional group reacting
with (A) and/or (B).
[0126] More particularly suitable are also HALS compounds of the
general formula (III):
##STR00009## [0127] in which [0128] R.sup.21 is OH, SH, NHR or
NH.sub.2, [0129] R.sup.22 is H, C.sub.1-C.sub.22 alkyl,
C.sub.1-C.sub.8 alkoxy, [0130] R.sup.23, R.sup.24, R.sup.25, and
R.sup.26 independently of one another, identically or differently,
are C.sub.1-C.sub.22 alkyl, or R.sup.23 and R.sup.24 and/or
R.sup.25 and R.sup.26 together with the carbon atom to which they
are attached form a 4-, 5-, 6-, 7- or 8-membered ring, [0131]
R.sup.27 and R.sup.28 independently of one another, identically or
differently, are H or C.sub.1-C.sub.22 alkyl [0132] and [0133]
R.sup.21 reacts with (A) and/or (B).
[0134] With very particular preference R.sup.21.dbd.OH,
R.sup.22.dbd.R.sup.23.dbd.R.sup.24.dbd.R.sup.25.dbd.R.sup.26=methyl,
and R.sup.27.dbd.R.sup.28.dbd.H.
[0135] In one embodiment of the present invention, mixtures of the
invention comprise hyperbranched polycarbonates with stabilizing
groups, a characteristic feature of which is that these
polycarbonates have a dynamic viscosity in the range from 100 to
150 000 mPas, preferably up to 10 000 mPas, determined at
23.degree. C., for example in accordance with DIN 53019.
[0136] In one embodiment of the present invention, mixtures of the
invention comprise hyperbranched polycarbonates with stabilizing
groups, a characteristic feature of which is that these
polycarbonates have a number average molecular weight (M.sub.n) of
from 100 to 15 000 g/mol, preferably from 200 to 12 000 g/mol and
in particular from 400 to 10 000 g/mol, which can be determined,
for example, by means of GPC, polymethyl methacrylate (PMMA) as
standard and dimethylacetamide as eluent.
[0137] In one embodiment of the present invention, mixtures of the
invention comprise hyperbranched polycarbonates with stabilizing
groups, a characteristic feature of which is that these
polycarbonates have a glass transition temperature T.sub.g in the
range from -70 to 10.degree. C., determined by differential
thermoanalysis (differential scanning calorimetry).
[0138] In one embodiment of the present invention, mixtures of the
invention comprise hyperbranched polycarbonates with stabilizing
groups, a characteristic feature of which is that these
polycarbonates have an OH number in the range from 0 to 600 mg
KOH/g, preferably from 1 to 550 mg KOH/g and in particular from 1
to 500 mg KOH/g (in accordance with DIN 53240, part 2).
[0139] In one preferred embodiment of the present invention,
mixtures of the invention comprise hyperbranched polycarbonates
with stabilizing groups, with the characteristic feature that these
polycarbonates have a dynamic viscosity in the range from 100 to
150 000 mPas, preferably to 10 000 mPas, determined at 23.degree.
C., in accordance for example with DIN 53019, and that these
polycarbonates have a number-average molecular weight (M.sub.n) of
100 to 15 000, preferably of 200 to 12 000, and more particularly
of 400 to 10 000 g/mol, which can be determined, for example, by
means of GPC, polymethyl methacrylate (PMMA) as standard and
dimethylacetamide as eluent, and that these polycarbonates have a
glass transition temperature T.sub.g in the range from -70.degree.
C. to 10.degree. C., determined by differential thermoanalysis
(differential scanning calorimetry), and that these polycarbonates
have an OH number in the range from 0 to 600, preferably 1 to 550,
and more particularly from 1 to 500 mg KOH/g (in accordance with
DIN 53240, part 2).
[0140] For the preparation of hyperbranched polycarbonate it is
also possible optionally to add one or more compounds (D) having
two alcoholic hydroxyl groups per molecule, for which the
abbreviated term compounds (D) is also used. Examples of suitable
compounds (D) comprise ethylene glycol, diethylene glycol,
triethylene glycol, 1,2- and 1,3-propanediol, dipropylene glycol,
tripropylene glycol, neopentyl glycol, 1,2-, 1,3-, and
1,4-butanediol, 1,2-, 1,3-, and 1,5-pentanediol, hexanediol,
cyclopentanediol, cyclohexanediol, cyclohexanedimethanol,
bis(4-hydroxycyclohexyl)methane, bis(4-hydroxycyclohexyl)ethane,
2,2-bis(4-hydroxycyclohexyl)propane,
1,1'-bis(4-hydroxyphenyl)-3,3-5-trimethylcyclohexane, resorcinol,
hydroquinone, 4,4'-dihydroxyphenyl, bis-(4-bis(hydroxyphenyl)
sulfide, bis(4-hydroxyphenyl) sulfone, bis(hydroxymethyl)benzene,
bis(hydroxymethyl)toluene, bis(p-hydroxyphenyl)methane,
bis(p-hydroxyphenyl)ethane, 2,2-bis(p-hydroxyphenyl)propane,
1,1-bis(p-hydroxy-phenyl)cyclohexane, dihydroxybenzophenone,
bifunctional polyether polyols based on ethylene oxide, propylene
oxide, butylene oxide, or a mixture thereof, polytetra-hydrofuran,
polycaprolactone, or polyesterols based on diols and dicarboxylic
acids.
[0141] In another embodiment, hyperbranched polycarbonates
comprised in the mixtures of the invention can comprise not only
the functional groups already obtained by means of the reaction
(hydroxyl groups, carbonate groups or carbamoyl chloride groups)
but also one or more further functional groups. The
functionalization can be effected during the
molecular-weight-increase process, or subsequently, i.e., after the
actual poly-condensation is at an end.
[0142] If components which have not only hydroxyl or carbonate
groups but also further functional groups or functional elements
are added before or during the actual formation of the
polycarbonates by polycondensation, a hyperbranched polycarbonate
polymer having randomly distributed functionalities different from
the carbonate, carbamoyl chloride or hydroxyl groups is
obtained.
[0143] By way of example, these effects can be achieved by adding,
during polycondensation, compounds bearing not only hydroxyl
groups, carbonate groups or carbamoyl chloride groups but also
further functional groups or functional elements, such as mercapto
groups, primary, secondary or tertiary amino groups, ether groups,
carboxylic acid groups or derivatives thereof, sulfonic acid groups
or derivatives thereof, phosphonic acid groups or derivatives
thereof, silane groups, siloxane groups, aryl radicals or
long-chain alcohol radicals. Examples of compounds that can be used
for modification by means of carbamate groups are ethanolamine,
propanolamine, isopropanolamine, 2-(butylamino)ethanol,
2-(cyclohexylamino)ethanol, 2-amino-1-butanol,
2-(2''-amino-ethoxy)ethanol, or higher alkoxylation products of
ammonia, 4-hydroxypiperidine, 1-hydroxyethylpiperazine,
diethanolamine, dipropanolamine, diisopropanolamine,
tris(hydroxymethyl)aminomethane, tris(hydroxyethyl)aminomethane,
ethylenediamine, propylenediamine, hexamethylenediamine, or
isophoronediamine.
[0144] An example of a compound that can be used for modification
by mercapto groups is mercaptoethanol. Tertiary amino groups can be
produced by, for example, incorporation of triethanolamine,
tripropanolamine, N-methyldiethanolamine, N-methyl-dipropanolamine
or N,N-dimethylethanolamine. Ether groups can, for example, be
generated by cocondensation of bifunctional or higher-functional
polyetherols. Addition of dicarboxylic acids, tricarboxylic acids,
dicarboxylic esters, for example dimethyl terephthalate, or
tricarboxylic esters can produce ester groups. Reaction with
long-chain alkanols or alkanediols can introduce long-chain alkyl
radicals. Reaction with alkyl or aryl diisocyanates generates
polycarbonates which have alkyl, aryl and urethane groups, and
addition of primary or secondary amines leads to introduction of
urethane or urea groups.
[0145] Subsequent functionalization can be obtained by reacting the
hyperbranched poly-carbonate according to the invention in an
additional process step with a suitable functionalization reagent
which can react with the OH and/or carbonate or carbamoyl chloride
groups of the polycarbonate.
[0146] Inventive hyperbranched polycarbonates comprising hydroxyl
groups can, for example, be modified by addition of molecules
comprising acid groups or comprising isocyanate groups. By way of
example, polycarbonates comprising acid groups can be obtained by
reaction with compounds comprising anhydride groups. Furthermore,
inventive hyper-branched polycarbonates comprising hydroxyl groups
can also be converted to high-functionality polycarbonate polyether
polyols by reaction with alkylene oxides, for example ethylene
oxide, propylene oxide or butylene oxide.
[0147] A preferred procedure in the preparation of hyperbranched
polycarbonates comprising stabilizing groups (b) mixes [0148] (A)
at least one compound having at least three alcoholic hydroxyl
groups per molecule [0149] (B) with at least one reagent of the
general formula I, [0150] (C) with at least one reagent of the
general formula X.sup.3-(A.sup.1).sub.m-X.sup.4 [0151] (D) and, if
appropriate, with at least one compound having two alcoholic
hydroxyl groups per molecule and heats the mixture to a temperature
in the range from 60 to 260.degree. C., preferably 80 to
220.degree. C.
[0152] The reaction of compound (A) with reagent (B) and reagent
(C) can be carried out in one step. However, it can also be carried
out in two steps, and, by way of example, compound (A) can firstly
be reacted with reagent (B) to produce a hyperbranched
polycarbonate and this can then be functionalized with reagent
(C).
[0153] In the reaction with reagent (B), H--X.sup.1 and H--X.sup.2
are usually eliminated. When H--X.sup.1 and/or H--X.sup.2 are/is
hydrogen halide, in particular HCl, the hydrogen halide(s)
eliminated is/are preferably removed from the reaction mixture by
addition of a base, for example in equimolar amounts based on
hydrogen halide to be eliminated. Suitable bases are, for example,
alkali metal hydroxides or organic amines, in particular tertiary
amines, such as triethylamine and Hunig base
(diisopropylethylamine). When H--X.sup.1 and H--X.sup.2 are
alcohols, the alcohol(s) H--X.sup.1 and H--X.sup.2 eliminated
is/are preferably removed by distillation, preferably during the
reaction. The removal by distillation can be carried out at
atmospheric pressure or under reduced pressure, for example at 0.1
to 950 mbar, in particular at 100 to 900 mbar. The distillation is
preferably carried out at atmospheric pressure.
[0154] The preparation process of the hyperbranched polycarbonates
comprising stabilizing groups (b) can be carried out in the
presence of an organic solvent which is preferably aprotic.
Examples are decane, dodecane, or solvent naphtha, also aromatic
hydro-carbons, such as toluene, ethylbenzene, one or more isomeric
xylenes, or chlorinated aromatic hydrocarbons, such as
chlorobenzene. Also suitable are ethers having a sufficiently high
boiling point, for example di-n-butyl ether or 1,4-dioxane. Further
suitable solvents are N,N-dimethylformamide and
N,N-dimethylacetamide. However, the preparation of the
hyperbranched polycarbonates comprising stabilizing groups (b) is
preferably carried out without use of solvents.
[0155] The preparation process of the hyperbranched polycarbonates
comprising stabilizing groups (b) can be carried out in the
presence of a catalyst or a catalyst mixture. Suitable catalysts
are compounds which catalyze esterification or transesterification
reactions, for example alkali metal hydroxides, alkali metal
carbonates, alkali metal hydrogencarbonates, preferably of sodium,
potassium or cesium, or organic amines, in particular tertiary
amines, guanidines, ammonium compounds, phosphonium compounds,
organic compounds of aluminum, tin, zinc, titanium, zirconium or
bismuth, and also double metal cyanide (DMC) catalysts as
described, for example, in DE 10138216 or DE 10147712.
[0156] Preference is given to use of potassium hydroxide, potassium
carbonate, potassium hydrogencarbonate, sodium hydroxide, sodium
carbonate, sodium hydrogencarbonate, 1,4-diazabicyclo[2.2.2]octane
(DABCO), diazabicyclononene (DBN), diazabicyclo-undecene (DBU),
imidazoles, such as imidazole, 1-methylimidazole or
1,2-dimethyl-imidazole, titanium tetra-n-butylate, titanium
tetraisopropylate, dibutyltin oxide, dibutyltin dilaurate, tin
dioctoate, zirconium acetylacetonate, or mixtures thereof.
[0157] The amount added of the catalyst or catalyst mixture is
generally from 50 to 10 000 ppm by weight, preferably from 100 to
5000 ppm by weight, based on the amount of compound (A) used or the
entirety of (A) and (D).
[0158] In general the hyperbranched polycarbonates comprising
stabilizing groups (b) are prepared in a pressure range from 0.1
mbar to 20 bar, preferably at 1 mbar to 5 bar.
[0159] The preparative process is for example carried out in
reactors or reactor cascades which are operated batchwise,
semicontinuously or continuously, for example in one or more
tanks.
[0160] A hyperbranched polycarbonate can be prepared using:
from 10 to 59 mol % of compound (A), preferably from 10 to 55 mol
%, and more preferably up to 49 mol %, of compound (A), from 40 to
60 mol % of reagent (B), preferably from 45 to 55 mol %, and more
preferably about 50 mol %, of reagent (B), from 1 to 50 mol % of
reagent (C), preferably up to 45 mol %, and more preferably up to
40 mol %, of reagent (C), in each case based on the total reaction
mixture of (A), (B), and (C).
[0161] The amount of the compound or compounds (D) used is normally
from 0 to 50 mol %, based on the compound (A), preferably from 0 to
45 mol %, more preferably up to 40 mol %, and very preferably from
0 to 30 mol %.
[0162] By virtue of the abovementioned setting of the reaction
conditions and, if appropriate, by virtue of the selection of the
suitable solvent, hyperbranched polycarbonates comprising
stabilizing groups (b) and obtained in the form of crude product
can be further processed after the preparation process, without
further purification.
[0163] The hyperbranched polycarbonate according to the invention
obtained as crude product can additionally be stripped, i.e., freed
of low molecular weight, volatile compounds. For this purpose, the
catalyst can optionally be deactivated after the desired conversion
has been reached and the low molecular weight volatile
constituents, e.g., monoalcohols, phenols, carbonates, hydrogen
chloride, or volatile oligomeric or cyclic compounds, can be
removed by distillation, if appropriate with introduction of a gas,
preferably nitrogen, carbon dioxide or air, if appropriate under
reduced pressure.
[0164] There are various possible ways of stopping the
intermolecular polycondensation reaction of the preparative process
of the hyperbranched polycarbonates comprising stabilizing groups
(b). For example, the temperature can be reduced to a range in
which the reaction ceases and the hyperbranched polycarbonate is
storage-stable. In another embodiment, the catalyst or catalyst
mixture can be deactivated--in the case of basic catalysts by, for
example, addition of an acidic component, a Lewis acid, for
example, or an organic or inorganic protic acid.
[0165] The reaction can also be stopped automatically when the
number of terminal functional groups available for further reaction
becomes insufficient by virtue of reaction with reagent (C).
[0166] Moreover, as soon as a hyperbranched polycarbonate is
present with the desired degree of polycondensation, the reaction
can be stopped by adding a product with groups reactive toward
hyperbranched polycarbonate comprising stabilizing groups (b). By
way of example, a mono-, di- or polyamine can be added or, for
example, a mono-, di- or polyisocyanate, a compound comprising
epoxy groups, or an acid derivative which is reactive with OH
groups.
[0167] Particularly preferred as component (b) of the mixtures of
the invention are those hyperbranched carbonates, comprising
stabilizing groups, in which as many as possible, and particularly
all, of the substituents, symbols, and indices adopt their
preferred or particularly preferred definition.
[0168] In a further preferred embodiment of the mixture of the
invention the branched polymer comprises urethane, allophanate,
urea, biuret, uretdione, amide, isocyanurate, carbodiimide,
uretonimine, oxadiazinetrione or iminooxadiazinedione groups and is
referred to in the context of the present invention as a branched
polyisocyanate. Preferably there are urethane, allophanate, urea
and/or biuret groups comprised.
[0169] Di- and polyisocyanates comprise an average of from 2 to 10,
preferably from 2.1 to 10, more preferably from 2.2 to 8,
isocyanate groups per molecule. Polyfunctional isocyanates are di-
or polyisocyanates or their mixtures.
[0170] Di- and polyisocyanates which are suitable are the prior-art
aliphatic, cycloaliphatic, and aromatic isocyanates or mixtures
thereof. Preferred di- or polyisocyanates are diphenylmethane
4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, the mixtures
composed of monomeric diphenylmethane diisocyanates and of
oligomeric diphenyl-methane diisocyanates (polymeric MDI), tolylene
2,4-diisocyanate, tolylene 2,6-diisocyanate, naphthylene 1,5- and
2,6-diisocyanate, phenylene 1,3- and 1,4-diisocyanate, diphenyl
diisocyanate, toluidine diisocyanate, triisocyanatotoluene,
tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone
diisocyanate, methylenebis(cyclohexyl) 2,4'- or 4,4'-diisocyanate,
o-, m-, or p-xylylene diisocyanate, tetramethylxylylene
diisocyanate, dodecyl diisocyanate, lysine alkyl ester
diisocyanate, where alkyl is C.sub.1 alkyl to C.sub.10 alkyl,
2,2,4- or 2,4,4-trimethylhexamethylene 1,6-diiso-cyanate,
1,4-diisocyanatocyclohexane, 4-isocyanatomethyloctamethylene
1,8-diiso-cyanate, 2-butyl-2-ethylpentamethylene diisocyanate,
2-isocyanatopropylcyclohexyl isocyanate,
3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate, 1,3- or
1,4-bis-(isocyanatomethyl)cyclohexane,
1,4-diisocyanato-4-methylpentane, and 4-methyl-cyclohexane
1,3-diisocyanate (H-TDI).
[0171] It is preferable to use mixtures composed of two or more of
the above-mentioned polyisocyanates.
[0172] Suitable branched polyisocyanates are compounds which can be
prepared from the abovementioned di- or polyisocyanates or their
mixtures via linking by means of urethane, allophanate, urea,
biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine,
oxadiazinetrione, or iminooxadiazinedione structures. These linking
mechanisms are described for example in Becker and Braun,
Kunststoff-Handbuch Nr. 7 [Plastics Handbook No. 7], Polyurethane
[Polyurethanes], Carl-Hanser-Verlag Munich 1993. It is preferable
to use polyisocyanates which contain urethane structures,
allophanate structures, urea structures, biuret structures,
isocyanurate structures, uretonimine structures, oxadiazinetrione
structures, or iminoxadiazinedione structures.
[0173] It is also possible to use mixtures of the abovementioned
branched polyisocyanates as a basis for component (b) of the
mixture of the invention.
[0174] The linkage of the di- or polyisocyanates by way of urethane
groups takes place for example with use of alcohols or alcohol
mixtures whose functionality is 2 or greater. By way of example,
mention may be made of the reaction of 3 mol of hexamethylene
diisocyanate, isophorone diisocyanate, tolylene diisocyanate, or
diphenylmethylene diisocyanate with .ltoreq.1 mol of triol, such as
glycerol or trimethylolpropane, or else the reaction of two mol of
an oligomeric diphenylmethane diisocyanate (polymeric MDI) with
.ltoreq.1 mol of diol, such as ethylene glycol, butanediol,
hexanediol, or with a polyoxy-alkylenediol. These reactions form
branched polyisocyanates whose functionality is greater than 2. In
this connection see also Becker and Braun, Kunststoff-Handbuch Nr.
7 [Plastics Handbook No. 7], Polyurethane [Polyurethanes],
Carl-Hanser-Verlag Munich 1993, page 91.
[0175] Polyisocyanates comprising allophanate groups are produced
from polyisocyanates comprising urethane groups by reacting the
urethane groups with further isocyanate groups. In this connection,
see also Becker and Braun, Kunststoff-Handbuch Nr. 7 [Plastics
Handbook No. 7], Polyurethane [Polyurethanes], Carl-Hanser-Verlag
Munich 1993, page 94. Another preparation route is the reaction of
oxadiazinetriones with alcohols according to EP 825211. By way of
example for the preparation of an allophanate, mention may be made
of the reaction of hexamethylene diisocyanate or isophorone
diisocyanate with monoalcohols, which according to GB 994 890, EP
496 208, EP 524 500, or EP 524 501 give oligoisocyanates whose
functionality is greater than 2. Mention may also be made of the
reaction of hexamethylene diisocyanate or isophorone diisocyanate
with di- or polyhydric alcohols, as described by way of example in
EP 1122273. These reactions form branched polyisocyanates having
functionality greater than 2.
[0176] By way of example, polyisocyanates comprising urea groups
and comprising biuret groups may be prepared via reactions of
isocyanates with water or with amines. In this connection see also
Becker and Braun, Kunststoff-Handbuch Nr. 7 [Plastics Handbook No.
7], Polyurethane [Polyurethanes], Carl-Hanser-Verlag Munich 1993,
page 95. By way of example, mention may be made of the reaction of
hexamethylene diisocyanate or isophorone diisocyanate with water or
with water-generating substances, as are described in DE-A 28 08
801, DE-A 34 03 277, or DE-A 15 43 178. These reactions form
branched polyisocyanates having functionality greater than 2.
[0177] Polyisocyanates comprising isocyanurate structures are
obtained by catalytic or thermal cyclization of three isocyanate
groups. If di- or polyisocyanates are used as starting compounds,
the products are generally not only the actual trimers but also
higher oligomeric polyisocyanates. The overall functionality of
these polyisocyanates is therefore greater than 3. In this
connection see also Becker and Braun, Kunststoff-Handbuch Nr. 7
[Plastics Handbook No. 7], Polyurethane [Polyurethanes],
Carl-Hanser-Verlag Munich 1993, page 91. By way of example, mention
may be made of the preparation of branched polyisocyanates via
isocyanuratization of hexamethylene diisocyanate or of isophorone
diisocyanate, a possible method for which is that according to DE-A
29 16 201 or DE-A 38 10 908.
[0178] Polyisocyanates comprising uretonimine groups are obtained
via further reaction of isocyanate groups with polyisocyanates
comprising carbodiimide groups. In this connection see also Becker
and Braun, Kunststoff-Handbuch Nr. 7 [Plastics Handbook No. 7],
Polyurethane [Polyurethanes], Carl-Hanser-Verlag Munich 1993, page
94.
[0179] Polyisocyanates comprising oxadiazinetrione groups are
obtained via reaction of di- or polyisocyanates with carbon
dioxide, as described for example in DE-A 16 70 666.
[0180] Polyisocyanates comprising iminooxadiazinedione groups can
be regarded as asymmetric relatives of the polyisocyanates
comprising isocyanurate groups. The preparation of these compounds
is described for example in DE-A 197 34 048.
[0181] Preferably use is made of aliphatic or cycloaliphatic
branched di- or polyisocyanates which comprise isocyanurate,
urethane, allophanate, urea or biuret groups.
[0182] The branched polyisocyanates comprised in the mixtures of
the invention comprise one or more stabilizing groups, with
stabilized additives corresponding to the stabilizing groups being
coupled to the polyisocyanates via functional groups which are able
to react chemically with the NCO groups of the polyisocyanates and
in so doing to form a covalent bond.
[0183] One class of stabilizing groups which act as antioxidants
are sterically hindered phenol groups. Corresponding sterically
hindered phenol groups have already been described above for the
case of the hyperbranched polycarbonates and are also used for the
case of the branched polyisocyanates. The sterically hindered
phenol groups preferred in the case of the hyperbranched
polycarbonates are also preferred in the case of the branched
polyisocyanates.
[0184] A further group of stabilizing groups which function as
light stabilizers are based on HALS compounds. Corresponding HALS
groups or HALS compounds have already been described above for the
case of the hyperbranched polycarbonates and are also used for the
case of the branched polyisocyanates. The HALS groups or HALS
compounds preferred in the case of the hyperbranched polycarbonates
are also preferred in the case of the branched polyisocyanates.
[0185] A further group of stabilizing groups are aromatic amine
groups. Corresponding aromatic amine groups have already been
described above for the case of the hyperbranched polycarbonates
and are also used for the case of the branched polyisocyanates. The
aromatic amine groups preferred in the case of the hyperbranched
polycarbonates are also preferred in the case of the branched
polyisocyanates.
[0186] In a further embodiment of the mixture of the invention the
branched polyisocyanates comprise two different stabilizing groups,
one of these groups being based on sterically hindered phenols and
the other being based on HALS compounds.
[0187] The branched polyisocyanates comprising stabilizing groups
are typically prepared by way of a polyaddition reaction such that
at least one branched polyisocyanate as anchor group is introduced
as an initial charge in a reaction vessel, if appropriate with the
further use of an organic solvent, under an inert gas atmosphere,
preferably under nitrogen, and this initial charge is brought to
reaction temperature with stirring. Subsequently, at reaction
temperature, at least one stabilizing group is added continuously
or discontinuously. The amount of stabilizing group is dependent on
the number of NCO groups of the branched polyisocyanate and is
preferably selected such that the ratio of the molar number of
isocyanate groups to the molar number of groups of the active
substance that are reactive therewith is substantially 1:1. Where
two or more active substances are reacted simultaneously or
successively with the poly-isocyanate, the total amount of the
reactive groups of the active substances is made such that it
corresponds substantially to the total amount of the isocyanate
groups. The branched polyisocyanates thus prepared, comprising
stabilizing groups, may, however, also have up to 20 mol %,
preferably up to 10 mol %, of free NCO groups, i.e., NCO groups
which have not been consumed by reaction with the stabilizing
group. Preferably, however, the stabilizers of the invention have
substantially no free NCO groups.
[0188] The reaction time is generally selected such that the NCO
groups of the branched polyisocyanates are reacted completely with
the reactive groups of the stabilizing group. The aforementioned
reaction with the stabilizing groups and the auxiliaries may take
place, if appropriate, in the presence of catalysts, which are used
in amounts of 0.0001% to 1% by weight, more particularly of 0.001%
to 0.1% by weight, based in each case on the amount of the branched
polyisocyanates. Suitable catalysts for polyaddition reactions
include organometallic compounds, especially organotin, organozinc,
organotitanium, organobismuth or organozirconium compounds.
Particular preference is given to using, for example, dibutyltin
dilaurate, dibutyltin oxide, titanium tetrabutylate, zinc
acetylacetonate or zirconium acetylacetonate. Additionally it is
possible to use strong bases, preferably nitrogen compounds, such
as tributylamine, quinuclidine, diazabicyclooctane,
diazabicyclononane, diazabicyclononene, diaza-bicycloundecane or
diazabicycloundecene.
[0189] Suitable solvents which can be used are those which are
inert toward the reactants under reaction conditions. Suitability
is possessed for example by acetone, 2-butanone, ethyl acetate,
butyl acetate, tetrahydrofuran, dioxane, benzene, toluene, xylene,
ethyl-benzene, chlorobenzene, dichlorobenzene, dimethylformamide,
dimethylacetamide or N-methylpyrrolidone.
[0190] The reaction temperature for the polyaddition reaction is
typically -10 to 220.degree. C., preferably 0 to 180.degree. C. The
reaction takes place both at atmospheric pressure and at a pressure
above or else below atmospheric pressure, such as, for example, at
a pressure of 2 to 20 bar or at 0.1 to 0.001 bar.
[0191] In one embodiment of the present invention, mixtures of the
invention comprise branched polyisocyanates with stabilizing
groups, of which a characteristic feature is that these
polyisocyanates have a dynamic viscosity in the range from 100 to
150 000 mPas, preferably up to 10 000 mPas, determined at
40.degree. C., in analogy for example to DIN 53019.
[0192] In one embodiment of the present invention, mixtures of the
invention comprise branched polyisocyanates with stabilizing
groups, a characteristic feature of which is that these
polyisocyanates have a number-average molecular weight (M.sub.e) of
100 to 15 000, preferably of 200 to 12 000, and more particularly
of 400 to 10 000 g/mol, which can be determined, for example, by
GPC, polymethyl methacrylate (PMMA) as standard and tetrahydrofuran
as eluent.
[0193] In one preferred embodiment of the present invention,
mixtures of the invention comprise branched polyisocyanates having
stabilizing groups, a characteristic feature of which is that these
polyisocyanates have a dynamic viscosity in the range from 100 to
150 000 mPas, preferably up to 10 000 mPas, determined at
40.degree. C., in analogy for example to DIN 53019, and that these
polyisocyanates have a number-average molecular weight (M.sub.n) of
100 to 15 000, preferably of 200 to 12 000, and more particularly
of 400 to 10 000 g/mol, which can be determined, for example, by
GPC, polymethyl methacrylate (PMMA) as standard and tetrahydrofuran
as eluent.
[0194] In one embodiment of the mixture of the invention the
polymer used as branched polymer comprising stabilizing groups is
the polymer obtained by the reaction of a mixture comprising:
[0195] (A') one or more polyfunctional isocyanates, [0196] (B') one
or more HALS compounds comprising a functional group reacting with
(A'), [0197] (C') inert solvent or mixtures of inert solvents,
[0198] (D') optionally catalyst.
[0199] In this system the isocyanate (A') preferably has a
functionality of more than 2 and more preferably the isocyanate
(A') is an oligomeric isocyanate based on hexa-methylene
diisocyanate or isophorone diisocyanate.
[0200] Preferably, furthermore, the HALS compound (B') is a
compound of the above-described general formula (III) where
R.sup.21 reacts with the polyfunctional isocyanate (A') or with the
NCO groups of the branched polyisocyanate.
[0201] With very particular preference R.sup.21.dbd.OH,
R.sup.22.dbd.R.sup.23.dbd.R.sup.24.dbd.R.sup.25.dbd.R.sup.26=methyl,
and R.sup.27.dbd.R.sup.28.dbd.H.
[0202] The inert solvent (C') is preferably acetone, 2-butanone,
tetrahydrofuran, ethyl acetate or butyl acetate.
[0203] The optional catalyst (D') is preferably dibutyltin
dilaurate, dibutyltin oxide or titanium tetrabutylate.
[0204] In the mixtures of the invention component (c) may further
comprise optionally one or more additions.
[0205] Optional further additions (c)
[0206] Optionally the mixture of the invention comprises as
component (c), or the inanimate organic material to be stabilized
by the mixture comprises, in addition, at least one further light
stabilizer and/or further (co)stabilizers. Suitable light
stabilizers and further (co)stabilizers are selected, for example,
from groups a) to s): [0207] a) 4,4-diarylbutadienes, [0208] b)
cinnamic esters, [0209] c) benzotriazoles, [0210] d)
hydroxybenzophenones, [0211] e) diphenylcyanoacrylates, [0212] f)
oxamides, [0213] g) 2-phenyl-1,3,5-triazines, [0214] h)
antioxidants, [0215] i) nickel compounds, [0216] j) sterically
hindered amines not attached as stabilizing groups to branched
polymer, [0217] k) metal deactivators, [0218] l) phosphites and
phosphonites, [0219] m) hydroxylamines, [0220] n) nitrones, [0221]
o) amine oxides, [0222] p) benzofuranones and indolinones, [0223]
q) thiosynergists, [0224] r) peroxide-destroying compounds, and
[0225] s) basic costabilizers.
[0226] Group a) of the 4,4-diarylbutadienes includes for example
compounds of the formula (aa)
##STR00010##
[0227] The compounds are known from EP-A-916 335. The substituents
R.sup.19 and R.sup.20, independently of one another, identically or
differently, are preferably C.sub.1-C.sub.8 alkyl and
C.sub.5-C.sub.8 cycloalkyl.
[0228] Group b) of the cinnamic esters includes for example
2-isoamyl 4-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate,
methyl .alpha.-methoxycarbonylcinnamate, methyl
.alpha.-cyano-.beta.-methyl-p-methoxycinnamate, butyl
.alpha.-cyano-.beta.-methyl-p-methoxycinnamate, and methyl
.alpha.-methoxycarbonyl-p-methoxycinnamate.
[0229] Group c) of the benzotriazoles includes for example
2-(2'-hydroxyphenyl)benzo-triazoles such as
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-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole,
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-
orobenzotriazole,
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)-benzotriaz-
ole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzo--
triazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydrox-
yphenyl)-benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole,
2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-yl-
phenol]; the product of esterifying
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotr-
iazole with polyethylene glycol 300; [R--CH2CH2--COO(CH2)3]2 where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl and
mixtures thereof.
[0230] Group d) of the hydroxybenzophenones includes for example
2-hydroxybenzophenones such as 2-hydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone,
2,2',4,4'-tetrahydroxybenzo-phenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxy-benzophenone,
2-hydroxy-4-(2-ethylhexyloxy)benzophenone,
2-hydroxy-4-(n-octyloxy)-benzophenone,
2-hydroxy-4-methoxy-4'-methylbenzophenone,
2-hydroxy-3-carboxy-benzophenone,
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium
salt, and
2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-bissulfonic acid and
its sodium salt.
[0231] Group e) of the diphenylcyanoacrylates includes for example
ethyl 2-cyano-3,3-diphenylacrylate, obtainable commercially for
example under the name Uvinul.RTM. 3035 from BASF AG, Ludwigshafen,
2-ethylhexyl 2-cyano-3,3-diphenylacrylate, obtainable commercially
for example as Uvinul.RTM. 3039 from BASF AG, Ludwigshafen, and
1,3-bis[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis{[Z-cyano-3',3'-diph-
enyl-acryloyl)oxy]methyl}propane, obtainable commercially for
example under the name Uvinul.RTM. 3030 from BASF AG,
Ludwigshafen.
[0232] Group f) of the oxamides includes for example
4,4'-dioctyloxyoxanilide, 2,2'-di-ethoxyoxanilide,
2,2'-dioctyloxy-5,5'-di-tert-butoxanilide,
2,2'-didodecyloxy-5,5'-di-tert-butoxanilide,
2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide,
2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with
2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, and also mixtures of
ortho-, para-methoxy-disubstituted oxanilides and mixtures of
ortho- and para-ethoxy-disubstituted oxanilides.
[0233] Group g) of the 2-phenyl-1,3,5-triazines includes for
example 2-(2-hydroxyphenyl)-1,3,5-triazines such as
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-
,
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazin-
e,
2-(2-hydroxy-4-octyloxy-phenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazi-
ne,
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tr-
iazine,
2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-d-
imethyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-
-1,3,5-triazine,
2-[4-(dodecyloxy/-tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(-
2,4-dimethylphenyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis-(2,4-dimeth-
ylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine,
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,
and
2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.
[0234] Group h) of the antioxidants comprises, for example:
Alkylated monophenols such as, for example,
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-butyl-phenol,
2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-(a-methylcyclohexyl)-4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol, unbranched or
sidechain-branched nonylphenols such as, for example,
2,6-dinonyl-4-methylphenol,
2,4-dimethyl-6-(1-methylundec-1-yl)phenol,
2,4-dimethyl-6-(1-methylheptadec-1-yl)-phenol,
2,4-dimethyl-6-(1-methyltridec-1-yl)phenol, and mixtures
thereof.
[0235] Alkylthiomethylphenols such as, for example,
2,4-dioctylthiomethyl-6-tert-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol and
2,6-didodecylthiomethyl-4-nonylphenol.
[0236] Hydroquinones and alkylated hydroquinones such as, for
example, 2,6-di-tert-butyl-4-methoxyphenol,
2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone,
2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone,
2,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyphenyl stearate, and
bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
[0237] Tocopherols, such as, for example, .alpha.-tocopherol,
.beta.-tocopherol, .gamma.-tocopherol, .delta.-tocopherol, and
mixtures thereof (vitamin E).
[0238] Hydroxylated thiodiphenyl ethers such as, for example,
2,2'-thiobis(6-tert-butyl-4-methylphenol),
2,2'-thiobis(4-octylphenol),
4,4'-thiobis(6-tert-butyl-3-methylphenol),
4,4'-thiobis(6-tert-butyl-2-methylphenol),
4,4'-thiobis(3,6-di-sec-amylphenol), and
4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.
[0239] Alkylidenebisphenols such as, for example,
2,2'-methylenebis(6-tert-butyl-4-methyl-phenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(.alpha.-methylcyclohexyl)phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl-4-methylphenol),
2,2'-methylenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(6-tert-butyl-4-isobutyl-phenol),
2,2'-methylenebis[6-(a-methylbenzyl)-4-nonylphenol],
2,2'-methylenebis-[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol],
4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-butyl-2-methylphenol),
1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)butane,
2,6-bis(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-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,
ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate],
bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclo-pentadiene,
bis[2-(3'-tert-butyl-2-hydroxy-5-methylbenzyl)-6-tert-butyl-4-methylpheny-
l] terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane,
2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecyl-mercaptobutan-
e,
1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
[0240] Benzyl compounds such as, for example,
3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxy-dibenzyl ether, octadecyl
4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl
4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,
tris(3,5-di-tert-butyl-4-hydroxybenzyl)-amine,
1,3,5-tri(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
di(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl
3,5-di-tert-butyl-4-hydroxybenzylmercapto-acetate,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol
terephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)
isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)
isocyanurate, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid
dioctadecyl ester, and 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric
acid monoethyl ester, calcium salt.
[0241] Hydroxybenzylated malonates such as, for example,
dioctadecyl 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,
dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,
didodecyl
mercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,
and
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]2,2-bis(3,5-di-tert-butyl-4-hydrox-
ybenzyl)-malonate.
[0242] Hydroxybenzyl aromatics such as, for example,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene,
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,
and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
[0243] Triazine compounds such as, for example,
2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triaz-
ine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-tr-
iazine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5--
triazine,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-phenylethyl)-1,3,5-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-tr-
iazine, and 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)
isocyanurate.
[0244] Benzylphosphonates such as, for example, dimethyl
2,5-di-tert-butyl-4-hydroxy-benzylphosphonate, diethyl
3,5-di-tert-butyl-4-hydroxybenzylphosphonate (diethyl
(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methylphosphonate),
dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl 5-tert-butyl-4-hydroxy-3-methyl-benzylphosphonate, and
the calcium salt of monoethyl
3,5-di-tert-butyl-4-hydroxy-benzylphosphonate.
[0245] Acylaminophenols such as, for example, 4-hydroxylauranilide,
4-hydroxystearanilide,
2,4-bisoctylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine,
and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
[0246] Esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with
monohydric or polyhydric alcohols, such as with methanol, ethanol,
n-octanol, isooctanol, octa-decanol, 1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol,
thiodiethylene glycol, diethylene glycol, triethylene glycol,
pentaerythritol, tris(hydroxyethyl) isocyanurate,
N,N'-bis(hydroxyethyl)oxalamide, 3-thiaundecanol,
3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0247] Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with
monohydric or polyhydric alcohols, such as with methanol, ethanol,
n-octanol, isooctanol, octa-decanol, 1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol,
thiodiethylene glycol, diethylene glycol, triethylene glycol,
pentaerythritol, tris(hydroxyethyl) isocyanurate,
N,N'-bis(hydroxyethyl)oxalamide, 3-thiaundecanol,
3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0248] Esters of .beta.-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic
acid with monohydric or polyhydric alcohols, such as with methanol,
ethanol, octanol, octadecanol, 1,6-hexane-diol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, and
4-hydroxymethyl-1-phospha-2,6,7-trioxa-bicyclo[2.2.2]octane.
[0249] Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with
monohydric or polyhydric alcohols, such as with methanol, ethanol,
octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene
glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, and
4-hydroxymethyl-1-phospha-2,6,7-trioxa-bicyclo[2.2.2]octane.
[0250] Amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylene-
diamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylened-
iamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,
N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxy-phenyl]propionyloxy)ethyl]oxam-
ide (e.g., Naugard.RTM.XL-1 from Uniroyal).
Ascorbic Acid (vitamin C)
[0251] Amine antioxidants, such as, for example,
N,N'-diisopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylenediamine,
N,N'-bis(1,4-dimethylpentyl)-p-phenylene-diamine,
N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,
N,N'-bis(1-methyl-heptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine,
N,N'-diphenyl-p-phenylenediamine,
N,N'-bis(2-naphthyl)-p-phenylenediamine,
N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,
N-cyclohexyl-N'-phenyl-p-phenylenediamine,
4-(p-toluenesulfamoyl)diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyldiphenylamine, 4-isopropoxy-diphenylamine,
N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,
N-phenyl-2-naphthylamine, octylated diphenylamine, for example,
p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol,
4-butyrylaminophenol, 4-nonanoyl-aminophenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
bis(4-methoxy-phenyl)amine,
2,6-di-tert-butyl-4-dimethylaminomethylphenol,
2,4'-diaminodiphenyl-methane, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetramethyl-4,4'-diaminodiphenyl-methane,
1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,
o-tolyl biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine,
tert-octylated N-phenyl-1-naphthyl-amine, a mixture of mono- and
dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-
and dialkylated nonyldiphenylamines, a mixture of mono- and
dialkylated dodecyldiphenylamines, a mixture of mono- and
dialkylated isopropyl/isohexyl-diphenylamines, a mixture of mono-
and dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a
mixture of mono- and dialkylated
tert-butyl/tert-octylphenothiazines, a mixture of mono- and
dialkylated tert-octylphenothiazines, N-allylphenothiazine,
N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,
N,N-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine,
2,2,6,6-tetramethylpiperidin-4-one,
2,2,6,6-tetramethylpiperidin-4-ol, the dimethyl succinate polymer
with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol [CAS number
65447-77-0], (for example, Tinuvin.RTM. 622 from Ciba Specialty
Chemicals, Inc.), polymer of
2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one
and epichlorohydrin [CAS No.: 202483-55-4], for example
(Hostavin.RTM. N 30 from Clairant).
[0252] Group i) of the nickel compounds includes for example nickel
complexes of 2,2'-thiobis[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-cyclohexyl-diethanolamine,
nickel dibutyl dithiocarbamate, nickel salts of
4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters
such as of the methyl or ethyl esters, for example, nickel
complexes of ketoximes such as, for example, of
2-hydroxy-4-methyl-phenyl undecyl ketoxime, and the nickel complex
of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, with or without
additional ligands.
[0253] Group j) of the sterically hindered amines includes for
example 4-hydroxy-2,2,6,6-tetra-methylpiperidine,
1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,
1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,
bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,
bis(2,2,6,6-tetramethyl-4-piperidyl) succinate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,
bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate,
bis(1,2,2,6,6-penta-methyl-4-piperidyl)
n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate
(n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid
bis(1,2,2,6,6-pentamethylpiperidyl) ester), condensation product of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid, linear or cyclic condensation products of
N,N'-bis(2,2,6,6-tetra-methyl-4-piperidyl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine,
tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,
tetrakis(2,2,6,6-tetra-methyl-4-piperidyl)
1,2,3,4-butanetetracarboxylate,
1,1'-(1,2-ethanediyl)bis-(3,3,5,5-tetramethylpiperazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyl-oxy-2,2,6,6-tetramethylpiperidine,
bis(1,2,2,6,6-pentamethylpiperidyl)
2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-tri-azaspiro[4.5]decane-2,4-dione,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or
cyclic condensation products of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product 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, condensation product of
2-chloro-4,6-di-(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-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,
mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine, condensation product of
N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation product
of 1,2-bis(3-aminopropylamino)ethane and
2,4,6-trichloro-1,3,5-triazine and also
4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[136504-96-6]);
N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecyl-succinimide,
N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane,
reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
and epichlorohydrin,
1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxy-phenyl-
)ethene, diester of 4-methoxymethylenemalonic acid with
1,2,2,6,6-pentamethyl-4-hydroxypiperidine,
poly[methylpropyl-3-oxo-4-(2,2,6,6-tetramethyl-4-piperidyl)]-siloxane,
1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperi-
dine, 1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,
2,6,6-tetramethylpiperidine, the reaction product of
1-oxyl-4-hydroxy-2,2,6,6-tetra-methylpiperidine and a carbon
radical of t-amyl alcohol,
1-(2-hydroxy-2-methyl-propoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine,
1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine,
bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-methylpiperidin-4-yl)
sebacate,
bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-methylpiperidin-
-4-yl) adipate,
bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-piperidin-4-yl)
succinate,
bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-piperidin-4-yl)
glutarate,
2,4-bis{N[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-methylpiperidin-4-y-
l]-N-butylamino}-6-(2-hydroxyethylamino)-s-triazine,
hexahydro-2,6-bis(2,2,6,6-tetramethyl-4-piperidyl)-1H,4H,5H,8H-2,3a,4a,6,-
7a,8a-hexaazacyclopenta-[def]fluorene-4,8-dione (e.g. Uvinul.RTM.
4049 from BASF AG, Ludwigshafen),
poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6-
,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4--
piperidinyl)imino]]) [CAS No. 71878-19-8],
1,3,5-triazine-2,4,6-triamine,
N,N'''-[1,2-ethanediylbis-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperid-
inyl)amino]-1,3,5-triazin-2-yl]imino]-3,1-propanediyl]]bis[N',N''-dibutyl--
N',N''-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) (CAS No.
106990-43-6) (e.g., Chimassorb 119 from Ciba Specialty Chemicals,
Inc.).
[0254] Group k) of the metal deactivators includes for example
N,N'-diphenyloxalamide, N-salicylal-N'-salicyloylhydrazine,
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-bisphenyl hydrazide, N,N'-diacetyladipic dihydrazide,
N,N'-bis(salicyloyl)oxalic dihydrazide, and
N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
[0255] Group l) of the phosphites and phosphonites includes for
example triphenyl phosphite, diphenyl alkyl phosphites, phenyl
dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl
phosphite, trioctadecyl phosphite, distearyl pentaerythritol
diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl
pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)
pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methyl-phenyl)
pentaerythritol diphosphite, diisodecyloxy pentaerythritol
diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol
diphosphite, bis(2,4,6-tris(tert-butylphenyl) pentaerythritol
diphosphite, tristearyl sorbitol triphosphite,
tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphonite,
6-isooctyloxy-2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxaphosphepi-
ne,
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenzo[d,g][1,3,2]dioxaph-
osphocine, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,
bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,
2,2',2''-nitrilo-[triethyl
tris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite],
and
2-ethylhexyl-(3,3',5,5'-tetra-tert-butyl-1,1-biphenyl-2,2'-diyl)phosphite-
.
[0256] Group m) of the hydroxylamines includes for example
N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine,
N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine,
N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine,
N,N-dioctadecyl-hydroxylamine,
N-hexadecyl-N-octadecylhydroxylamine,
N-heptadecyl-N-octadecyl-hydroxylamine,
N-methyl-N-octadecylhydroxylamine, and N,N-dialkylhydroxylamine
from hydrogenated tallow fatty amines.
[0257] Group n) of the nitrones includes 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.-tridecyl nitrone, N-hexadecyl
.alpha.-pentadecyl nitrone, N-octadecyl .alpha.-heptadecyl nitrone,
N-hexadecyl .alpha.-heptadecyl nitrone, N-octadecyl
.alpha.-pentadecyl nitrone, N-heptadecyl .alpha.-heptadecyl
nitrone, N-octadecyl .alpha.-hexadecyl nitrone, N-methyl
.alpha.-heptadecyl nitrone, and nitrones derived from
N,N-dialkylhydroxylamines prepared from hydrogenated talc fatty
amines.
[0258] Group o) of the amine oxides includes for example amine
oxide derivatives as described in U.S. Pat. Nos. 5,844,029 and
5,880,191, didecylmethylamine oxide, tridecylamine oxide,
tridodecylamine oxide, and trihexadecylamine oxide.
[0259] Group p) of the benzofuranones and indolinones includes for
example those described in U.S. Pat. Nos. 4,325,863; 4,338,244;
5,175,312; 5,216,052; 5,252,643; in DE-A-4316611; in DE-A-4316622;
in DE-A-4316876; in EP-A-0589839 or EP-A-0591102, or
3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-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-ethoxy-phenyl)benzofuran-2-one,
3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzo-furan-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, Irganoxs
HP-136 from Ciba Specialty Chemicals, and
3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
[0260] Group q) of the thiosynergists includes for example dilauryl
thiodipropionate or distearyl thiodipropionate.
[0261] Group r) of the peroxide-destroying compounds includes for
example esters of .beta.-thiodipropionic acid, for example, the
lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole
or the zinc salt of 2-mercaptobenzimidazole, zinc
dibutyldithio-carbamate, dioctadecyl disulfide, and pentaerythritol
tetrakis(.beta.-dodecylmercapto)-propionate.
[0262] Group s) of the basic costabilizers includes for example
melamine, polyvinyl-pyrrolidone, dicyandiamide, triallylcyanurate,
urea derivatives, hydrazine derivatives, amines, polyamides,
polyurethanes, alkali metal 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.
[0263] The mixture of the invention, as component (c), or the
plastic may further comprise other additives and additions t).
Suitable additives from the group t) are the customary additives,
such as pigments, dyes, nucleating agents, fillers, reinforcing
agents, antifogging agents, biocides, and antistats, for
example.
[0264] Suitable pigments are inorganic pigments, examples being
titanium dioxide in its three modifications--rutile, anatase or
brookite; ultramarine blue, iron oxides, bismuth vanadates or
carbon black, and also the class of the organic pigments, examples
being compounds from the class of the phthalocyanines, perylenes,
azo compounds, isoindolines, quinophthalones,
diketopyrrolopyrroles, quinacridones, dioxazines, and
indanthrones.
[0265] By dyes are meant all colorants which dissolve completely in
the plastic used or are present in a molecularly disperse
distribution and can therefore be used for the high-transparency,
nonscattering coloring of polymers. Likewise regarded as dyes are
organic compounds which exhibit a fluorescence in the visible part
of the electromagnetic spectrum, such as fluorescent dyes.
[0266] Suitable nucleating agents include for example inorganic
substances, examples being talc, metal oxides such as titanium
dioxide or magnesium oxide, phosphates, carbonates or sulfates,
preferably of alkaline earth metals; organic compounds such as
monocarboxylic or polycarboxylic acids and also their salts, such
as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid,
sodium succinate or sodium benzoate; and polymeric compounds, such
as ionic copolymers ("ionomers"), for example.
[0267] Suitable fillers and reinforcing agents include for example
calcium carbonate, silicates, talc, mica, kaolin, barium sulfate,
metal oxides and metal hydroxides, carbon black, graphite, wood
flour and flours or fibers of other natural products, and synthetic
fibers. Further suitable examples of fibrous or pulverulent fillers
include carbon or glass fibers in the form of glass fabrics, glass
mats or filament glass rovings, chopped glass, glass beads, and
wollastonite. Glass fibers can be incorporated either in the form
of short glass fibers or in the form of continuous fibers
(rovings).
[0268] Examples of suitable antistats include amine derivatives
such as N,N-bis(hydroxy-alkyl)alkylamines or -alkylenamines,
polyethylene glycol esters and ethers, ethoxylated carboxylic
esters and carboxamides, and glyceryl mono- and distearates, and
also mixtures thereof.
[0269] With preference there are antioxidants, flame retardants
and/or colorants comprised as optional component (c) in the
mixtures of the invention.
[0270] The weight ratio of components (a) and (b) in the mixtures
of the invention is generally from 5:1 to 1:5, preferably from 2:1
to 1:2, more preferably from 1.2:1 to 1:1.2, with more particular
preference being given to a mixture in the weight ratio of
approximately 1:1.
[0271] If component (c) is present, the weight ratio of the sum of
components (a) and (b) to component (c) in the mixtures of the
invention is generally from 100:1 to 2:1, preferably from 50:1 to
5:1, more preferably from 30:1 to 7:1, more particular preference
being given to a mixture in the weight ratio of approximately
10:1.
[0272] The mixtures of the invention can be prepared by known
processes familiar to the skilled worker.
[0273] For example, if component (b) is a solid, component (b) can
be added to the liquid component (a) with mixing.
[0274] If component (b) is itself liquid, then processes known to
the skilled worker for the mixing of liquids can be used for mixing
it with the liquid component (a).
[0275] In one preferred embodiment the mixture of the invention is
liquid.
[0276] Generally speaking the components (a), (b), and, optionally,
(c) can be mixed in any order.
[0277] For example, component (c) can be added to the mixture of
components (a) and (b), and the resulting mixture can then be
homogenized.
[0278] Alternatively components (c) may be admixed to (a) and/or
(b) first, and then the end mixture produced.
[0279] The invention also provides, accordingly, a corresponding
process for preparing the mixtures of the invention.
[0280] The mixtures of the invention may also only be produced in
the inanimate organic materials to be stabilized, by the addition
of components (a), (b), and, optionally, (c).
[0281] It may be advantageous to carry out the mixing of the
components at an elevated temperature. More particularly component
(a) and optionally component (c) may be added immediately after the
synthesis of component (b).
[0282] Particular preference is given to the following combinations
of compounds of components (a) and the branched polymers comprising
stabilizing groups (b) of the formulae IIa and IIb: [0283] 1.
2-Ethylhexyl 2-cyano-3,3-diphenylacrylate and compounds of the
formulae IIa or IIb based on 4-amino-2,2,6,6-tetramethylpiperidine,
[0284] 2. 2-Ethylhexyl 2-cyano-3,3-diphenylacrylate and compounds
of the formulae IIa or IIb based on
4-amino-1,2,2,6,6-pentamethylpiperidine, [0285] 3. 2-Ethylhexyl
2-cyano-3,3-diphenylacrylate and compounds of the formulae IIa or
IIb based on 4-hydroxy-2,2,6,6-tetramethylpiperidine, [0286] 4.
2-Ethylhexyl 2-cyano-3,3-diphenylacrylate and compounds of the
formulae IIa or IIb based on
4-hydroxy-1,2,2,6,6-pentamethylpiperidine, [0287] 5. 2-Ethylhexyl
2-cyano-3,3-diphenylacrylate and compounds of the formulae IIa or
IIb based on 4-amino-2,2,6,6-tetramethylpiperidine-N-oxyl, [0288]
6. 2-Ethylhexyl 2-cyano-3,3-diphenylacrylate and compounds of the
formulae IIa or IIb based on
4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, [0289] 7.
2-Ethylhexyl 4-methoxycinnamate and compounds of the formulae IIa
or IIb based on 4-amino-2,2,6,6-tetramethylpiperidine, [0290] 8.
2-Ethylhexyl 4-methoxycinnamate and compounds of the formulae IIa
or IIb based on 4-amino-1,2,2,6,6-pentamethylpiperidine, [0291] 9.
2-Ethylhexyl 4-methoxycinnamate and compounds of the formulae IIa
or IIb based on 4-hydroxy-2,2,6,6-tetramethylpiperidine, [0292] 10.
2-Ethylhexyl 4-methoxycinnamate and compounds of the formulae IIa
or IIb based on 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, [0293]
11. 2-Ethylhexyl 4-methoxycinnamate and compounds of the formulae
IIa or IIb based on 4-amino-2,2,6,6-tetramethylpiperidine-N-oxyl,
[0294] 12. 2-Ethylhexyl 4-methoxycinnamate and compounds of the
formulae IIa or IIb based on
4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl,
[0295] The mixtures of the invention are outstandingly suitable for
use as stabilizers for stabilizing inanimate organic material
against the effect of light, oxygen, and heat. The mixtures of the
invention are generally added to the inanimate organic materials to
be stabilized at a concentration sufficient to achieve the desired
stabilization effect (i.e., the effective amount). The mixtures of
the invention are added preferably in a concentration of 0.01% to
5% by weight, more preferably of 0.02% to 1% by weight, based on
the inanimate organic material, before, during or after the
production of the inanimate organic material.
[0296] The invention further provides a method of stabilizing
inanimate organic materials, more particularly plastics and coating
materials, against the effect of light, oxygen, and heat, which
comprises adding the mixtures of the invention to the inanimate
organic materials, preferably in the concentrations indicated
above.
[0297] The mixture of the invention may be added to the inanimate
organic material to be protected in the form of a prefabricated
mixture of components (a), (b), and, optionally, (c), although it
is likewise possible to add components (a), (b), and, optionally,
(c) separately to the material to be protected, in which case the
mixture is formed only in the material to be protected. In the case
where components (a), (b), and, optionally, (c) are added
separately they may be added simultaneously or at different times,
the sequence of addition generally being immaterial.
[0298] By inanimate organic material is meant, for example,
cosmetic products such as ointments and lotions, drug formulations
such as pills and suppositories, photographic recording material
such as photographic emulsions, or intermediates for plastics and
coating materials, but more particularly plastic and coating
materials themselves. From inanimate organic material it is
possible to produce articles.
[0299] The invention further provides inanimate organic material,
more particularly plastics and coating materials, which are
stabilized against the effect of light, oxygen, and heat and which
comprise the mixtures of the invention, preferably in the
concentrations indicated above.
[0300] For the mixing of the mixture of the invention primarily
with plastics it is possible to employ all known apparatus and
methods of mixing stabilizers or other adjuvants into polymers.
[0301] Examples of plastics which can be stabilized by means of the
mixtures of the invention include the following:
thermoplastic elastomers; polymers of mono- and diolefins, such as,
for example, low-density and high-density polyethylene,
polypropylene, linear polybut-1-ene, polyisoprene, polybutadiene,
and copolymers of mono- or diolefins, or mixtures of said polymers;
copolymers of mono- or diolefins with other vinyl monomers, such
as, for example, ethylene-alkyl acrylate copolymers, ethylene-alkyl
methacrylate copolymers, ethylene-vinyl acetate copolymers or
ethylene-acrylic acid copolymers; polystyrene and also copolymers
of styrene or .alpha.-methylstyrene with dienes and/or acrylic
derivatives, such as, for example, styrene-butadiene,
styrene-acrylonitrile (SAN), styrene-ethyl methacrylate,
styrene-butadiene-ethyl acrylate,
styrene-acrylonitrile-methacrylate, acrylonitrile-butadiene-styrene
(ABS) or methyl methacrylate-butadiene-styrene (MBS): halogenated
polymers, such as polyvinyl chloride, polyvinyl fluoride,
polyvinylidene fluoride, and their copolymers, for example;
polymers deriving from .alpha.,.beta.-unsaturated acids and their
derivatives, such as polyacrylates, polymethacrylates,
polyacrylamides, and polyacrylonitriles; polymers deriving from
unsaturated alcohols and amines and/or their acrylic derivatives or
acetals, such as polyvinyl alcohol and polyvinyl acetate, for
example; polyurethanes, polyamides, polyureas, polyesters,
polycarbonates, polysulfones, polyethersulfones, and
polyetherketones.
[0302] Additionally it is possible to use the mixtures of the
invention to stabilize coatings, industrial coatings for example.
Particular emphasis among these may be given to baking varnish
systems, more particularly vehicle finishes, preferably two-coat
finishes. Another field of use is that, for example, of coating
materials for the exterior coating of buildings, other
constructions or technical apparatus.
[0303] The mixtures of the invention may be added in solid or
dissolved form to the coating material. In this context their high
solubility in coating systems is a particular advantage.
[0304] The mixtures of the invention are preferably used to
stabilize thermoplastic elastomers, based for example on
polyolefins. The mixtures of the invention find use more
particularly in the stabilization of molding compounds comprising
the stated materials.
[0305] Another preferred field of use is the stabilization of
low-density and high-density polyethylene, and also of
polypropylene and polyamide, including, for example, fibers of said
polymers.
[0306] Likewise preferred is the use of the mixtures of the
invention for stabilizing plastics composed of at least one polymer
selected from thermoplastic elastomers, polyolefins, polystyrene,
copolymers of styrene or of .alpha.-methylstyrene, polyesters and
polyethers, polycarbonates, polyvinyl chloride, polyacrylates,
polymethacrylates, polyurethanes, and physical blends of the
aforementioned polymers.
[0307] The mixtures of the invention exhibit improved stabilization
of inanimate organic materials with respect to light with a high UV
fraction and/or high light intensity. Furthermore, the mixtures of
the invention are based on easily accessible starting materials. By
means of the mixtures of the invention it is possible to ensure
efficient protection of inanimate organic materials with respect to
oxygen or heat.
[0308] The above embodiments of the process of the invention, and
the examples below, exemplarily illustrate the present invention.
However, for a person skilled in the art, there are many further
variations of the process, and combinations of the features of the
process of the invention, that are conceivable without departing
the scope of the claims.
EXAMPLES
Example 1
Preparation of Mixtures of the Invention
[0309] 972 g of trimethylolpropane, randomly etherified with 1 mol
of ethylene oxide per mole of hydroxyl groups, 411 g of
1,2,2,6,6-pentamethylpiperidin-4-ol, and 709 g of diethyl carbonate
were charged to a reaction vessel equipped with stirrer, reflux
condenser, and internal thermometer, and then 0.2 g of potassium
carbonate was added and the mixture was heated to 140.degree. C.
with stirring and stirred at 140.degree. C. for 3.5 h. Thereafter
the reflux condenser was swapped for a descending condenser,
ethanol was removed by distillation, and the temperature of the
reaction mixture was slowly raised to 200.degree. C. The distillate
(490 g) was collected in a cooled, round-bottomed flask. Then the
reaction mixture was cooled to 140.degree. C., 0.1 g of 85%
strength phosphoric acid was added for deactivation, and the
mixture was then freed from volatiles at 100 mbar for 10 min.
Subsequently the product was cooled to room temperature and
analyzed by gel permeation chromatography; the eluent was
dimethylacetamide and the calibration standard used was polymethyl
methacrylate (PMMA). The number-average molecular weight, Mn, was
810 g/mol and the weight-average molecular weight, Mw, was 1590
g/mol. The viscosity, determined at 23.degree. C. in accordance
with DIN 53019, was 1100 mPas.
[0310] 500 g of the polycarbonate of the invention comprising
stabilizer groups were then heated to 80.degree. C., 500 g of
2-ethylhexyl 2-cyano-3,3-diphenylacrylate (CAS No. 6197-30-4) were
added, and the mixture was stirred to homogeneity for 2 h. The
viscosity of the stabilizer mixture, determined at 23.degree. C. in
accordance with DIN 53019, was 5800 mPas.
Example 2
Preparation of Mixtures of the Invention
[0311] A reaction vessel with stirrer, gas inlet tube, and dropping
funnel with pressure compensation was charged, under dry nitrogen
blanketing, with 588 g of BASONAT.RTM. HA 300, in solution in an
equal amount by weight of dry 2-butanone, 300 ppm (based on
isocyanate) of dibutyltin dilaurate were added at room temperature,
and the mixture was heated to 50.degree. C. Then 453.6 g of
1,2,2,6,6-pentamethylpiperidin-4-ol, in solution in the same amount
by weight of dry 2-butanone, were added dropwise over the course of
30 min. After the end of the addition the reaction mixture was
stirred at 50.degree. C. for 1 h more. Subsequently the solvent was
removed under reduced pressure on a rotary evaporator. The average
molar masses of the polymeric stabilizer were determined by means
of gel permeation chromatography (GPC). Elution was carried out
with tetrahydrofuran as the mobile phase, and the columns were
calibrated with polymethyl methacrylate as standard. Mn=1060 g/mol,
Mw=1190 g/mol.
[0312] 500 g of the polyurethane of the invention comprising
stabilizer groups were then heated to 80.degree. C. in a
round-bottomed flask, 500 g of 2-ethylhexyl
2-cyano-3,3-diphenylacrylate (CAS No. 6197-30-4) were added, and
the mixture was stirred to homogeneity for 2 h. The viscosity of
the stabilizer mixture, determined at 40.degree. C. in accordance
with DIN 53019, was 8100 mPas.
[0313] BASONAT.RTM. HA 300 (BASF AG): allophanate-group-comprising
polyisocyanate based on hexamethylene diisocyanate; the viscosity
at 23.degree. C. (DIN 53019) is 200-400 mPas.
* * * * *