U.S. patent application number 15/970095 was filed with the patent office on 2018-10-04 for use of protected n-hydroxyimide derivates and transition metal as oxygen scavenger system in transparent polyolefin films.
This patent application is currently assigned to BASF SE. The applicant listed for this patent is BASF SE. Invention is credited to Enrico Galfre, Edoardo Menozzi, Massimiliano Sala.
Application Number | 20180282046 15/970095 |
Document ID | / |
Family ID | 42154428 |
Filed Date | 2018-10-04 |
United States Patent
Application |
20180282046 |
Kind Code |
A1 |
Menozzi; Edoardo ; et
al. |
October 4, 2018 |
USE OF PROTECTED N-HYDROXYIMIDE DERIVATES AND TRANSITION METAL AS
OXYGEN SCAVENGER SYSTEM IN TRANSPARENT POLYOLEFIN FILMS
Abstract
An oxygen-scavenging composition containing (I) a polymeric
resin, (II) an organic oxidation additive based on a cyclic
oxyimide, (III) a metal salt, preferably a transition metal salt,
(IV) a sacrificial oxidizable substrate, and optionally, (V) an
additional component; wherein components (I) and (IV) are
different.
Inventors: |
Menozzi; Edoardo; (Basel,
CH) ; Sala; Massimiliano; (Casteinuovo Rangone (MO),
IT) ; Galfre; Enrico; (Basel, CH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen |
|
DE |
|
|
Assignee: |
BASF SE
Ludwigshafen
DE
|
Family ID: |
42154428 |
Appl. No.: |
15/970095 |
Filed: |
May 3, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15294805 |
Oct 17, 2016 |
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15970095 |
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14636490 |
Mar 3, 2015 |
9505541 |
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15294805 |
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13511162 |
Aug 20, 2012 |
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PCT/EP2010/068372 |
Nov 29, 2010 |
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14636490 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L 2201/08 20130101;
C08K 2201/012 20130101; C08L 2207/066 20130101; C08L 101/00
20130101; C08L 23/06 20130101; C08K 5/3437 20130101; C08K 5/42
20130101; C08K 5/005 20130101; C08K 5/3417 20130101; B65D 81/266
20130101; C08L 23/0815 20130101; C08K 5/098 20130101; C08L 23/0815
20130101; C08K 5/005 20130101; C08L 101/00 20130101 |
International
Class: |
B65D 81/26 20060101
B65D081/26; C08K 5/42 20060101 C08K005/42; C08L 23/08 20060101
C08L023/08; C08L 23/06 20060101 C08L023/06; C08K 5/3437 20060101
C08K005/3437; C08K 5/3417 20060101 C08K005/3417; C08K 5/098
20060101 C08K005/098; C08K 5/00 20060101 C08K005/00; C08L 101/00
20060101 C08L101/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 2, 2009 |
EP |
09177738.3 |
Claims
1. An oxygen-scavenging composition comprising (I) a polymeric
resin, (II) an organic oxidation additive based on a cyclic
oxyimide, (III) a metal salt, (IV) a sacrificial oxidizable
substrate, and optionally (V) an additional component; with the
proviso that components (I) and (IV) are different.
2. An oxygen-scavenging composition according to claim 1, wherein
component (II) is present in an amount of 0.001-10 wt %, based on
the polymeric resin, component (III) is present in an amount of
0.001-10 wt %, based on the polymeric resin, Component (IV) is
present in an amount of 0.001-10 wt %, based on the polymeric
resin, and optionally component (V) is present in an amount of
0.001-10 wt %, based on the polymeric resin.
3. The oxygen-scavenging composition according to claim 2, wherein
the polymeric resin is a thermoplastic polymer selected from the
group consisting of homopolymer of an olefin, a copolymer of olefin
monomers, copolymer of olefin monomer with diolefin monomer, cyclic
olefin, copolymer of one or more 1-olefin or diolefin with carbon
monoxide, copolymer of one or more 1-olefin and diolefin with
carbon monoxide, and polyvinyl alcohol.
4. The oxygen-scavenging composition according to claim 1, wherein
the organic oxidation additive is a compound selected from the
group consisting of N-(trityloxy)-phthalimide,
N-(stearoyloxy)phthalimide, N-(toluene-4-sulfonyloxy)-phthalimide,
N-(2-benzoylbenzoyloxy)-phthalimide, N,N'-dihydroxypyromellitic
diimine and N,N'-distearoyloxypyromelitimide.
5. The oxygen-scavenging composition according to claim 1, wherein
the metal salt is based on Co, Ce, Mn, Cu, Ni or Vd.
6. The oxygen-scavenging composition according to claim 1, wherein
the sacrificial oxidizable substrate is selected from the group
consisting of polybutadiene, polyester, squalane, squalene,
polystyrene, poly-limonene, poly alpha pinene, poly beta pinene,
poly-norbornene, polylactic acid and a mixture of linear and
branched alkyl chain C.sub.6-C.sub.30 alcohol.
7. The oxygen-scavenging composition according to claim 1, wherein
the sacrificial oxidizable substrate is a polyterpenic resin.
8. The oxygen-scavenging composition according to claim 1, wherein
the oxygen-scavenging composition further comprises one or more
additional components selected from the group consisting of filler,
reinforcing agent, pigment, light stabilizer, antioxidant, antislip
or antiblock additive, plasticizer, optical brightener, antistatic
agent and blowing agent.
9. The oxygen-scavenging composition according to claim 1, wherein
the organic oxidation additive is a cyclic oxyimide of the formula
(I) ##STR00056## wherein n is 1, 2 or 4; X is >C.dbd.O,
>S(O).sub.2 or >C(X.sub.1)(X.sub.2); X.sub.1 and X.sub.2
independently of one another are hydrogen, C.sub.1-C.sub.20 alkyl,
C.sub.3-C.sub.12 cycloalkyl unsubstituted or substituted by 1, 2 or
3 identic or different C.sub.1-C.sub.4 alkyl; or phenyl
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; Y
is C.sub.1-C.sub.30 alkyl, C.sub.2-C.sub.30 alkenyl,
C.sub.3-C.sub.12 cycloalkyl unsubstituted or substituted by 1, 2 or
3 C.sub.1-C.sub.4 alkyl; C.sub.5-C.sub.12 cycloalkenyl
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; a
bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms,
C.sub.7-C.sub.9 phenylalkyl unsubstituted or substituted on the
phenyl by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; diphenylmethyl
unsubstituted or substituted on the phenyl by 1, 2 or 3
C.sub.1-C.sub.4 alkyl; triphenylmethyl unsubstituted or substituted
on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; C.sub.2-C.sub.30
acyl, --COOY.sub.0, C.sub.1-C.sub.30 sulfonyl, --Si(Y.sub.1).sub.3
or --Si(OY.sub.2).sub.3; Y.sub.0, Y.sub.1 and Y.sub.2 independently
of one another are hydrogen, C.sub.1-C.sub.18 alkyl,
C.sub.3-C.sub.18 alkenyl, C.sub.3-C.sub.12 cycloalkyl which is
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl;
phenyl which is unsubstituted or substituted by 1, 2 or 3
C.sub.1-C.sub.4 alkyl; or C.sub.7-C.sub.9 phenylalkyl which is
unsubstituted or substituted on the phenyl by 1, 2 or 3
C.sub.1-C.sub.4 alkyl; and Z is an organic radical; with the
provisos that (1) when Y is C.sub.1-C.sub.30 alkyl,
C.sub.2-C.sub.30 alkenyl or C.sub.1-C.sub.30 sulfonyl, component
(I) is a polyolefin homo- or copolymer or a blend of a polyolefin
homo- or copolymer with another synthetic polymer; and (2) when n
is 2 or 4 and, at the same time, component (I) is a polyolefin
homo- or copolymer or a blend of a polyolefin homo- or copolymer
with another synthetic polymer, Y is additionally hydrogen.
10. A polymer article containing the oxygen-scavenging composition
according to claim 1.
11. The polymer article according to claim 10 which is a film, a
sheet or a laminate.
12. A polymer article which is a coextruded multilayer film
comprising: (A) a natural and/or a synthetic polymer and (B) an
organic oxidation additive based on a cyclic oxyimide of the
formula (I) ##STR00057## wherein n is 1, 2 or 4; X is >C.dbd.O,
>S(O).sub.2 or >C(X.sub.1)(X.sub.2); X.sub.1 and X.sub.2
independently of one another are hydrogen, C.sub.1-C.sub.20 alkyl,
C.sub.3-C.sub.12 cycloalkyl unsubstituted or substituted by 1, 2 or
3 identic or different C.sub.1-C.sub.4 alkyl; or phenyl
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; Y
is C.sub.1-C.sub.30 alkyl, C.sub.2-C.sub.30 alkenyl,
C.sub.3-C.sub.12 cycloalkyl unsubstituted or substituted by 1, 2 or
3 C.sub.1-C.sub.4 alkyl; C.sub.5-C.sub.12 cycloalkenyl
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; a
bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms,
C.sub.7-C.sub.9 phenylalkyl unsubstituted or substituted on the
phenyl by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; diphenylmethyl
unsubstituted or substituted on the phenyl by 1, 2 or 3
C.sub.1-C.sub.4 alkyl; triphenylmethyl unsubstituted or substituted
on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; C.sub.2-C.sub.30
acyl, --COOY.sub.0, C.sub.1-C.sub.30 sulfonyl, --Si(Y.sub.1).sub.3
or --Si(OY.sub.2).sub.3; Y.sub.0, Y.sub.1 and Y.sub.2 independently
of one another are hydrogen, C.sub.1-C.sub.18 alkyl,
C.sub.3-C.sub.18 alkenyl, C.sub.3-C.sub.12 cycloalkyl which is
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl;
phenyl which is unsubstituted or substituted by 1, 2 or 3
C.sub.1-C.sub.4 alkyl; or C.sub.7-C.sub.9 phenylalkyl which is
unsubstituted or substituted on the phenyl by 1, 2 or 3
C.sub.1-C.sub.4 alkyl; and Z is an organic radical; with the
provisos that (1) when Y is C.sub.1-C.sub.30 alkyl,
C.sub.2-C.sub.30 alkenyl or C.sub.1-C.sub.30 sulfonyl, component
(I) is a polyolefin homo- or copolymer or a blend of a polyolefin
homo- or copolymer with another synthetic polymer; and (2) when n
is 2 or 4 and, at the same time, component (I) is a polyolefin
homo- or copolymer or a blend of a polyolefin homo- or copolymer
with another synthetic polymer, Y is additionally hydrogen.
13. A polymer article according to claim 12 which is a food
packaging.
Description
[0001] There are many products which have to be kept in a closed
volume or packaged with little or almost no oxygen. These
oxygen-sensitive products include pharmaceuticals, food products,
meats, beverages, etc which are susceptible for degradation due to
the presence of oxygen. Limiting the exposure to oxygen provides a
means to maintain and enhance the quality and shelf-life of the
packaged product. The removal of oxygen from the packaged foods and
building barriers against oxygen penetration during storage
represents an important objective for the food packaging
technologist. For example packaging a food product in a package
capable of minimizing oxygen exposure is a means to maintain the
quality of the packaged product over an extended time and to retard
spoilage of the product so that it is maintained in inventory
longer without wastage and the need of restocking and
replacement.
[0002] In the food packaging industry, several techniques have been
developed to limit oxygen sensitive packaged materials to oxygen
exposure. Such techniques include the use of barrier material (with
low permeability to oxygen) as part of the packaging; the inclusion
of some items capable of consuming oxygen other then the packaging
material (through the use of sachets with material capable of
reacting with oxygen); and the creation of a reduced oxygen
environment within the package (e.g. modified atmosphere
packaging--MAP--and vacuum packaging). Even if each of the above
techniques has its place in the industry, it is well recognized
that the inclusion of an oxygen scavenger as a part of the
packaging article is one of the most desirable way of limiting
oxygen exposure.
[0003] Product sensitive to oxygen, particularly foods, beverages
and medicines, deteriorate or spoil in the presence of oxygen. One
approach to reducing these difficulties is to package such products
with packaging materials containing at least one layer of a
so-called "passive" gas barrier film that can act as a physical
barrier to transmission of oxygen but does not react with oxygen.
Films obtained from ethylene vinyl alcohol copolymer (EVOH) or
polyvinylidene dichloride (PVDC) are commonly used for this purpose
due to their excellent oxygen barrier properties. By physically
blocking transmission of oxygen, these barrier films can maintain
over time the initial oxygen levels within a package. Because
passive barrier films can add cost to a packaging construction and
do not reduce levels of oxygen already present in the packaging
construction, however, there is a need for effective, lower cost
alternatives and improvements.
[0004] An approach to achieving or maintaining a low oxygen
environment inside a package is to use a packet containing an
oxygen absorbent material. The packet, also sometimes referred to
as a pouch or sachet, is placed in the interior of the package
along with the product. Sakamoto et al. discloses oxygen absorbent
packets in Japan Laid Open Patent Application No. 121634/81 (1981).
A typical ingredient used in the oxygen scavenger carried in the
packet is reduced iron powder which can react with oxygen to form
ferrous oxide or ferric oxide, as disclosed in the U.S. Pat. No.
4,856,650. Also, is known to include in the packet, along with
iron, a reaction promoter such as sodium chloride, and a
water-absorbing agent, such as silica gel, as described in the U.S.
Pat. No. 4,992,410. Japan Laid Open Patent Application No. 82-24634
(1982) discloses an oxygen absorber composition comprising 100
parts by weight (pbw) iron powder, 2 to 7 pbw ammonium chloride, 8
to 15 pbw aqueous acid solution and 20 to 50 pbw of a slightly
water soluble filler such as activated clay. Japan Laid Open Patent
Application No. 79-158386 (1979) discloses an oxygen arresting
composition comprising a metal, such as iron, copper or zinc, and
optionally, a metal halide such as sodium chloride or zinc chloride
at a level of 0.001 to 100 pbw to 1 pbw of metal and a filler such
as clay at a level of 0.01 to 100 pbw to 1 pbw of metal.
[0005] Although oxygen absorbent or scavenger materials used in
packets can react chemically with oxygen in the package, also
sometimes referred to as "headspace oxygen", they do not prevent
external oxygen from penetrating into the package. Therefore, it is
common for packaging in which such packets are used to include
additional protection such as wrappings or passive barrier films of
the type described above. This adds costs to product costs. With
many easy-to-prepare foods, another difficulty with oxygen
scavenger packets is that consumers may mistakenly open them and
consume their contents together with the food. Moreover, the extra
manufacturing step of placing a packet into a container can slow
production. Further, oxygen absorbent packets are not useful with
liquid products.
[0006] In view of these disadvantages and limitation, it has been
proposed to incorporate directly into the walls of a packaging
article a so-called "active" oxygen absorber, i.e., one that reacts
with oxygen. Because such a packaging article is formulated to
include a material that reacts with oxygen permeating its walls,
the packaging is said to provide an "active-barrier" as
distinguished from passive barrier films which block transmission
of oxygen but do not react with it. Active-barrier packaging is an
attractive way to protect oxygen-sensitive products because it not
only can prevent oxygen from reaching the product from the outside
but also can absorb oxygen present within a container.
[0007] One approach for obtaining active-barrier packaging is to
incorporate a mixture of an oxidizable metal (e.g., iron) and an
electrolyte (e.g., sodium chloride) into a suitable resin, melt
process the result into monolayer or multilayer sheets or films and
form the resulting oxygen scavenger-containing sheets or films into
rigid or flexible containers or other packaging articles or
components. This type of active-barrier is disclosed in Japan Laid
Open Patent Application No. 56-60642 (1981), directed to an
oxygen-scavenging sheet composed of a thermoplastic resin
containing iron, zinc or copper and a metal halide. Disclosed
resins include polyethylene and polyethylene terephthalate. Sodium
chloride is the preferred metal halide. Component proportions are
such that 1 to 500 parts metal halide are present per 100 parts
resin and 1 to 200 parts metal halide are present per 100 part
metal. Similarly, the U.S. Pat. No. 5,153,038 discloses plastic
multilayer vessels of various layer structures formed from a resin
composition formed by incorporating an oxygen scavenger, and
optionally a water absorbing agent, in a gas barrier resin. The
oxygen scavenger can be a metal powder such as iron, low valence
metal oxides or reducing metal compounds. The oxygen scavenger can
be used in combination with an assistant compound such as a
hydroxide, carbonate, sulfite, thiosulfite, tertiary phosphate,
secondary phosphate, organic acid salt or halide of an alkali metal
or alkaline earth metal. The water absorbing agent can be an
inorganic salt such as sodium chloride, calcium chloride, zinc
chloride, ammonium chloride, ammonium sulfate, sodium sulfate,
magnesium sulfate, disodium hydrogenphosphate, sodium
dihydrogenphosphate, potassium carbonate or sodium nitrate. The
oxygen scavenger can be present at 1 to 1000 weight-% based on
weight of the barrier resin. The water absorbing agent can be
present at 1 to 300 weight-% based on weight of the barrier
resin.
[0008] One difficulty with scavenger systems incorporating an
oxidizable metal (e.g., iron) and a metal halide (e.g., sodium
chloride) into a thermoplastic layer is the inefficiency of the
oxidation reaction. To obtain sufficient oxygen absorption in
active-barrier packaging, high loadings of scavenger composition
are often used. This typically requires that sheets, films and the
other packaging layers or wall structures containing a scavenging
composition to be relatively thick. This, in turn, contributes to
cost of packaging material and may preclude attainment of thin
packaging films having adequate oxygen-scavenging capabilities.
[0009] Another oxygen-scavenging composition, disclosed in the U.S.
Pat. No. 4,104,192, comprises a dithionite and at least one
compound having water of crystallization or water of hydration.
Listed among these compounds are various hydrated sodium salts,
including carbonate, sulfate, sulfite and phosphates; sodium
pyrophosphate decahydrate is specifically mentioned. As disclosed
in Table 1, Example 1 of the patent, sodium pyrophosphate
decahydrate was the least effective of the compounds tested. In
addition, use of hydrate containing compounds may not suitable in
oxygen-scavenging resins that require high temperature processsing.
The U.S. Pat. No. 5,744,056, U.S. Pat. No. 6,369,148 and U.S. Pat.
No. 6,586,514 describe an oxygen scavenging composition comprising
an oxidizable metal component, an electrolyte component, and a
non-electrolytic acidifying component that is thermally stable at
thermoplastic resin melt fabrication temperatures. WO2006089895
discloses a similar system wherein the electrolytic component
participating in the oxidation reaction is obtained by hydrolysis
of a Lewis acid salts and/or theirs adducts.
[0010] One difficulty with scavenger systems of this type is the
relative inefficiency of the oxidation reaction within the polymer
matrix. In fact one molecule of iron generally absorbs only one
molecule of oxygen thus the scavenger active system must be
employed usually at high loading, leading to cost, compatibility,
transparency and color issues. In EP-A-1423456, for example, the
concentration of the metal is limited to less than 0.25% in order
to obtain a more transparent plastic object, limiting significantly
its effectiveness.
[0011] A different approach to oxygen scavenger technology employed
in synthetic thermoplastics such as polyolefin homo- and copolymers
include the use of conventional degradation additives such as
transition metal salts based on cobalt, copper or nickel which work
well in many applications were oxygen uptake is required. In this
case the polymer matrix itself act as oxidizable substrate and the
oxygen scavenger process has to proceed via oxidation reactions
along the carbon-carbon polyolefin chain catalyzed by the redox
cycle of polyvalent metal ions. Many countries have however
restrictive regulations on the use of such transition metals for
reasons of environmental concern.
[0012] A catalytic systems for the oxidation of organic substrates
based on N-hydroxy phthalimide (NHPI) both with and without metal
salts as co-catalysts is described in J. Org. Chem. 1996, 61,
4520-4526.
[0013] The Chemistry Vol. 56, No.7, 18-23, 2001 and Journal of
Synthetic Organic Chemistry, Vol. 59, No. 1, 4-12, 2001 disclose
that an N-hydroxyimide compound that coexists with various metal
salts reacts with oxygen contained in the air to serve as an
oxidation catalyst for alkane, alkene, and alcohol. WO 2005/010101
is related to the use of such autoxidation promoters for oxygen
absorbents containing oxidizable polymers for packaging
materials.
[0014] JP-A-2000-290312 describes a method in which various
polymers are denatured with gas containing oxygen atoms using an
N-hydroxyimide compound as a catalyst. This method allows a polar
group to be introduced efficiently into a polymer without cutting
the main chain of the polymer and as a result, a polymer can be
obtained that is excellent in antistatic property.
[0015] These oxidation reactions, however, are allowed to occur in
the presence of a polar solvent such as acetic acid, etc., i.e. in
the presence of a solvent that absorbs oxygen actively. These
reactions are oxidation reactions that occur between a liquid phase
and a liquid phase or between a solid phase and a liquid phase and
therefore are predicated on the intervention of transition metal
and the flow of a catalyst that occurs in the liquid. On the other
hand, it is required that the oxygen-absorbing material maintains
its solid state even when it absorbs oxygen. Accordingly, the
reaction that is required to take place in the oxygen-absorbing
material is the reaction that occurs between the solid phase and
the vapor phase. However, possibilities of the occurrence of such a
reaction have not been studied at all.
[0016] Thus, while a variety of approaches to maintaining or
reducing oxygen levels in packaged items have been advanced, there
remains a need for improved oxygen-scavenging composition and
packaging materials utilizing the same.
[0017] An object of the present invention is therefore to provide
improved oxygen-scavenging compositions and packagings. Another
object is to provide low costs, oxygen-scavenging compositions of
improved efficiency. Another object is to provide oxygen scavenging
composition that can be used effectively, even at relatively low
levels, in a wide range of active-barrier packaging films and
sheets, including laminated and coextruded multilayer films and
sheets. Another object is ti provide active-barrier packaging
containers that can increase the shelf-life of oxygen-sensitive
products by slowing the passage of external oxygen into the
container, by absorbing oxygen present inside the container or
both. Other objects will be apparent to those skilled in the
art.
[0018] The problem which was solved within this invention required
the use of thermal stable protected cyclic N-hydroxyimide
derivatives, transition metal catalyst in combination with an
oxidazable substrate like, but not limited at, polyterpene resin
based on alfa and/or beta pinene and/or d-limonene used as
organocatalytic oxidation additives for transparent food packaging
oxygen scavenger application. Besides several examples which
describe the use of the catalysts per se, examples of suitable
catalyst precursors are also given which make use of light,
humidity, and/or heat to trigger the initiation of the degradation
process. The catalytic role of the organic oxidation promoter is
summarized in the scheme below considering N-hydroxyphthalimide as
example compound:
##STR00001##
[0019] By designing cyclic N-hydroxyimide derivatives according to
the resin needs, the polarity can be easily adjusted changing the
substitution pattern of the basic nucleus. Unpolar resins such as
polyolefins will require lipophilic substituents, such as branched
and linear alkyl chains, whereas cyclic N-hydroxyimides designed
for more polar resins such as polyvinyl alcohol may be modified
attaching more hydrophilic groups such as polyethylene glycol or
polyhydroxy compounds such as sugars.
[0020] Particular attention is given when the hydrogen of the
N-hydroxy moiety of the cyclic imides is replaced by different
substituents. For this class of molecules the formation of the
active nitroxyl radical species, which is active towards the
oxidation of organic substrates, can be triggered by heat, light
and/or humidity, wherein the oxidation of the polymer can occur
independently both in presence or in absence of a transition metal
catalyst, other cocatalysts, radical initiators, photosensitisers
or -initiators, primary oxidants or mixture of thereof.
##STR00002##
[0021] The following oligomeric and monomeric molecules represent
examples of the above concept:
[0022] Monomeric NHPI derivatives:
##STR00003##
[0023] Oligomeric NHPI derivatives:
##STR00004##
[0024] The final products can be any type of plastic product for
food packaging application, which needs enhanced oxygen scavenger
activities. For example, the polymer component may be used to
manufacture mono or multilayer plastic films, sheets, laminates,
trays, bottles, styrofoam cups, blister packages, boxes, package
wrappings. The articles may be manufactured by any process
available to those of ordinary skill in the art including, but not
limited to, extrusion, extrusion blowing, film casting, film
blowing, calendering, injection molding, blow molding, compression
molding, thermoforming, spinning, blow extrusion and rotational
casting.
[0025] The cyclic N-hydroxyimide derivatives, transition metal
catalyst, oxidazable substrate and optionally other additional
components can be admixted with the polymer component either
simultaneously or in succession, or also immediately prior to the
actual processing step.
[0026] Thus the present invention relates to an oxygen-scavenging
composition comprising:
[0027] (I) A polymeric resin preferably a thermoplastic polymers
as:
[0028] homo- and copolymers of olefin monomers such as ethylene and
propylene, but also higher 1-olefins such as 1-butene, 1-pentene,
1-hexene or 1-octen. Preferred is polyethylene LDPE and LLDPE, HDPE
and polypropylene;
[0029] homo- and copolymers of olefin monomers with diolefin
monomers such as butadiene, isoprene and cyclic olefins such as
norbornene;
[0030] copolymers of one ore more 1-olefins and/or diolefins with
carbon monoxide and/or with other vinyl monomers, including, but
not limited to, acrylic acid and its corresponding acrylic esters,
methacrylic acid and its corresponding esters, vinyl acetate, vinyl
alcohol, vinyl ketone, styrene, maleic acid anhydride and vinyl
chloride;
[0031] polyvinyl alcohol;
[0032] (II) An organic oxidation additives based on a cyclic
oxyimide core as defined below, particularly on the compounds given
in the following tables:
TABLE-US-00001 Example 1 2 3 Structure N-(trityloxy)-phthalimide
##STR00005## N-(stearoyloxy)phthalimide ##STR00006##
N-(toluene-4-sulfonyloxy)- phthalimide ##STR00007##
TABLE-US-00002 Example 4 5 6 Structure N-(2-benzoylbenzoyloxy)-
phtalimide ##STR00008## N,N'- dihydroxypyromellitic diimide
##STR00009## N,N'-distearoyloxypyromelitimide ##STR00010##
[0033] Some further Examples are:
##STR00011##
[0034] The oxidation additive(s) may be present in total in a
concentration from 0.001-10 wt %, preferably 0.01-5 wt % and most
preferably 0.1-5 wt % based on the polymeric resin;
[0035] (III) Metal salts based on Co, Ce, Mn, Cu, Ni, Vd.
Preferably these salts are metal salts of fatty acids with a carbon
number raging from C.sub.12 to C.sub.36. Most preferred are metal
carboxylates of palmitic (C.sub.16), stearic (C.sub.18), oleic
(C.sub.18), linolic (C.sub.18) and linoleic (C.sub.18) acids.
Preferably the transition metal salt is Manganese which may be
present in a total concentration from 0.001-10 wt %, preferably
0.01-5 wt % and most preferably 0.1-5 wt % based on the polymeric
resin. Also possible are aromatic acids such as benzoic acid.
Examples for the use of these salts are given in U.S. Pat. No.
3,840,512 and U.S. Pat. No. 4,101,720;
[0036] (IV) Sacrificial oxidizable substrates like polybutadiene,
polyester, squalane, squalene, polystyrene, poly-limonene, poly
alpha pinene, poly beta pinene, polynorbornene, polylactic acid,
mixture of linear and branched alkyl chains alcohol (R:
C.sub.6-C.sub.30) can be employed. Preferably these oxidizable
substrates are present in a total concentration from 0.001-10 wt %,
preferably 0.01-5 wt % and most preferably 0.1-5 wt % based on the
polymeric resin; and optionally,
[0037] (V) additional components.
[0038] The optional additional components includes:
[0039] fillers and reinforcing agents such as calcium carbonate,
silicas, glass fibres, glass bulbs, talc, kaolin, mica, barium
sulfate, metal oxides and hydroxides, carbon black, graphite, wood
flour, flours of other natural products, synthetic fibers,
stearates used as fillers such as calcium stearate on zinc
stearate;
[0040] pigments such as carbon black, titanium dioxide in its rutil
or anatase forms, and other color pigments;
[0041] light stabilizers, antioxidants and/or further light
stabilizers such as e.g.:
[0042] 1. Alkylated monophenols, 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-butylphenol,
2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-(.alpha.-methylcyclohexyl)-4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are
linear or branched in the side chains, for example,
2,6-di-nonyl-4-methylphenol,
2,4-dimethyl-6-(1'-methylundec-1'-1'-yl)phenol,
2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures
thereof.
[0043] 2. Alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-tert-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-di-dodecylthiomethyl-4-nonylphenol.
[0044] 3. Hydroquinones and alkylated hydroquinones, 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,
bis(3,5-di-cert-butyl-4-hydroxyphenyl) adipate.
[0045] 4. Tocopherols, for example .alpha.-tocopherol,
.beta.-tocopherol, .gamma.-tocopherol, .delta.-tocopherol and
mixtures thereof (vitamin E).
[0046] 5. Hydroxylated thiodiphenyl ethers, 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),
4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.
[0047] 6. Alkylidenebisphenols, for example
2,2'-methylenebis(6-tert-butyl-4-methylphenol),
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-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-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-methylphenyl)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-methyl-phenyl)-3-n-dodecylmercaptobutane-
, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)
butyrate],
bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,
bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphe-
nyl]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-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,
1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
[0048] 7. O-, N- and S-benzyl compounds, for example
3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,
octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,
tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,
tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,
bis(3,5-di-cert-butyl-4-hydroxybenzyl)sulfide,
isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
[0049] 8. Hydroxybenzylated malonates, for example
dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,
di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,
di-dodecylmercaptoethyl-2,2-bis
(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydro-
xybenzyl)malonate.
[0050] 9. Aromatic hydroxybenzyl compounds, for example
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
[0051] 10. Triazine compounds, 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-hydroxyanilino)-1,3,5-tri-
azine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-t-
riazine,
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-hydroxyphenylethyl)-1,3,5-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-tr-
iazine,
1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
[0052] 11. Benzylphosphonates, for example
dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the
calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
[0053] 12. Acylaminophenols, for example 4-hydroxylauranilide,
4-hydroxystearanilide, octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
[0054] 13. Esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,
i-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)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0055] 14. Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol,
n-octanol, i-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)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dim-
ethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.
[0056] 15. Esters of
.beta.-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols, e.g. 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(hydroxylethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0057] 16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid
with mono- or polyhydric alcohols, e.g. 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)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0058] 17. Amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethyle-
nediamide,
N,N-bis(3,5-di-tert-butyl-4-hydroxyphenylpionyl)trimethylenedia-
mide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,
N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxami-
de (Naugard.RTM.XL-1, supplied by Uniroyal).
[0059] 18. Ascorbic acid (vitamin C)
[0060] 19. Aminic antioxidants, for example
N,N'-di-isopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylenediamine,
N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,
N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,
N,N'-bis(1-methylheptyl)-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-isopropoxydiphenylamine,
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-nonanoylaminophenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
bis(4-methoxyphenyl)amine,
2,6-di-tert-butyl-4-dimethylaminomethylphenol,
2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane,
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-naphthylamine, 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/isohexyldiphenylamines, a mixture of mono-
and dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-di-methyl-4H-1,4-benzothiazine, phenothiazine, a
mixture of mono- and dialkylated
tert-butyl/tert-octylphenothiazines, a mixture of mono- and
dialkylated tert-octyl-phenothiazines, N-allylphenothiazine,
N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene.
[0061] 20. 2-(2'-Hydroxyphenyl)benzotriazoles, for example
2-(2'-hydroxy-5'-methylphenyl)-benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole,
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole,
2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole,
2-(3',5'-bis-(.alpha.,.alpha.-dimethylbenzyl)-2'-hydroxyphenyl)benzotriaz-
ole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chl-
oro-benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-
-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-b-
enzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazo-
le,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotr-
iazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyp-
henyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole,
2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-y-
lphenol]; the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotr-
iazole with polyethylene glycol 300;
[R--CH.sub.2CH.sub.2--COO--CH.sub.2--CH.sub.2CH.sub.2 .sub.2, where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl,
2-[2'-hydroxy-3'-(.alpha.,.alpha.-dimethylbenzyl)-5'-(1,1,
3,3-tetramethylbutyl)-phenyl]benzotriazole;
2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(.alpha.,.alpha.-dimethylb-
enzyl)-phenyl]benzotriazole.
[0062] 21. 2-Hydroxybenzophenones, for example the 4-hydroxy,
4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,
4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
[0063] 22. Esters of substituted and unsubstituted benzoic acids,
for example 4-tert-butyl-phenyl salicylate, phenyl salicylate,
octylphenyl salicylate, dibenzoyl resorcinol,
bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol,
2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate,
hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl
3,5-di-tert-butyl-4-hydroxybenzoate,
2-methyl-4,6-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate.
[0064] 23. Acrylates, for example ethyl
.alpha.-cyano-.beta..beta.-diphenylacrylate, isooctyl
.alpha.-cyano-.beta..beta.-diphenylacrylate, methyl
.alpha.-carbomethoxycinnamate, methyl
.alpha.-cyano-.beta.-methyl-p-methoxycinnamate, butyl
.alpha.-cyano-.beta.-methyl-p-methoxy-cinnamate, methyl
.alpha.-carbomethoxy-p-methoxycinnamate,
N-(.beta.-carbomethoxy-.beta.-cyanovinyl)-2-methylindoline,
neopentyl tetra(.alpha.-cyano-.beta.,.beta.-diphenylacrylate.
[0065] 24. Sterically hindered amines, for example carbonic acid
bis(1-undecyloxy-2,2,6,6-tetra-methyl-4-piperidyl)ester,
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-pentamethyl-4-piperidyl)
n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate
of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid, linear or cyclic condensates of
N,N'-bis(2,2,6,6-tetramethyl-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-tetramethyl-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-stearyloxy-2,2,6,6-tetramethylpiperidine,
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-bu-
tylbenzyl)malonate,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]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 condensates of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane, the condensate of
2-chloro-4,6-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,
a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of
1,2-bis(3-aminopropylamino)ethane and
2,4,6-trichloro-1,3,5-triazine as well as
4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[136504-96-6]); a condensate of 1,6-hexanediamine and
2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and
4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[192268-64-7]);
N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,
N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane,
a 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-methoxyphenyl)-
ethene,
N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethy-
lenediamine, a diester of 4-methoxymethylenemalonic acid with
1,2,2,6,6-pentamethyl-4-hydroxypiperidine,
poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,
a reaction product of maleic acid anhydride-.alpha.-olefin
copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or
1,2,2,6,6-pentamethyl-4-aminopiperidine,
2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-N-butylami-
no]-6-(2-hydroxyethyl)amino-1,3,5-triazine,
1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperi-
dine, 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone,
Sanduvor (Clariant; CAS Reg. No. 106917-31-1],
5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, the
reaction product of
2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s-t-
riazine with N,N'-bis(3-aminopropyl)ethylenediamine),
1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazine-3-one-4-yl)amino-
)-s-triazine,
1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazine-3-one-4-yl)ami-
no)-s-triazine.
[0066] 25. Oxamides, for example 4,4'-dioctyloxyoxanilide,
2,2'-diethoxyoxanilide, 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, mixtures of o- and
p-methoxy-disubstituted ox-anilides and mixtures of o- and
p-ethoxy-disubstituted oxanilides.
[0067] 26. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example
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-octyloxyphenyl)-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-butyloxypropoxy)phenyl]-4,6-bis(2,4-di-
methyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethy-
l)-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-dimethy-
lphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-hexyloxy)phenyl-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,
2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis-
(2,4-dimethylphenyl)-1,3,5-triazine,
2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxyphenyl)-1,3,5-tr-
iazine.
[0068] processing additives such as antislip/antiblock additives,
plasticizers, optical brighteners, antistatic agents and blowing
agents;
[0069] antioxidants may be present in amounts to stabilize the
polymer during processing and forming steps, however large
quantities are undesired in order not to prevent degradation;
[0070] The present invention relates in particular to a polymer
article having accelerated oxygen scavenger properties triggered by
light and/or heat and/or humidity and made of a composition
containing:
[0071] (A) a natural and/or a synthetic polymer, preferably based
on homo- and copolymers of olefin monomers and
[0072] (B) a degradation accelerator based on a cyclic oxyimide of
the formula (I)
##STR00012##
[0073] wherein
[0074] n is 1, 2 or 4;
[0075] X is>C.dbd.O, >S(O).sub.2 or
>C(X.sub.1)(X.sub.2);
[0076] X.sub.1 and X.sub.2 independently of one another are
hydrogen, C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.12 cycloalkyl
unsubstituted or substituted by 1, 2 or 3 identic or different
C.sub.1-C.sub.4 alkyl; or phenyl unsubstituted or substituted by 1,
2 or 3 C.sub.1-C.sub.4 alkyl;
[0077] Y is C.sub.1-C.sub.30 alkyl, C.sub.2-C.sub.30 alkenyl,
C.sub.3-C.sub.12 cycloalkyl unsubstituted or substituted by 1, 2 or
3 C.sub.1-C.sub.4 alkyl; C.sub.5-C.sub.12 cycloalkenyl
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; a
bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms,
C.sub.7-C.sub.9 phenylalkyl unsubstituted or substituted on the
phenyl by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; diphenylmethyl
unsubstituted or substituted on the phenyl by 1, 2 or 3
C.sub.1-C.sub.4 alkyl; triphenylmethyl unsubstituted or substituted
on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; C.sub.2-C.sub.30
acyl, --COOY.sub.0, C.sub.1-C.sub.30 sulfonyl, --Si(Y.sub.1).sub.3
or --Si(OY.sub.2).sub.3;
[0078] Y.sub.0, Y.sub.1 and Y.sub.2 independently of one another
are hydrogen, C.sub.1-C.sub.18 alkyl, C.sub.3-C.sub.18 alkenyl,
C.sub.3-C.sub.12 cycloalkyl which is unsubstituted or substituted
by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; phenyl which is unsubstituted
or substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; or
C.sub.7-C.sub.9 phenylalkyl which is unsubstituted or substituted
on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4 alkyl;
[0079] and
[0080] Z is an organic radical;
[0081] with the provisos that
[0082] (1) when Y is C.sub.1-C.sub.30 alkyl, C.sub.2-C.sub.30
alkenyl or C.sub.1-C.sub.30 sulfonyl, component (A) is a polyolefin
homo- or copolymer or a blend of a polyolefin homo- or copolymer
with another synthetic polymer; and
[0083] (2) when n is 2 or 4 and, at the same time, component (A) is
a polyolefin homo- or copolymer or a blend of a polyolefin homo- or
copolymer with another synthetic polymer, Y is additionally
hydrogen.
[0084] The radical Y is preferably different from hydrogen.
[0085] According to one of the preferred embodiments, Z is an
organic radical containing one or more aromatic groups.
[0086] When n is 1, Z is in particular a group of the formula
(I-a), (I-b), (I-c), (I-d), (I-e), (I-f), (I-g), (I-h), (I-i),
(I-j), (I-k), (I-I), (I-m) or (I-n)
##STR00013## ##STR00014##
[0087] the aromatic rings of the formulae (I-a) to (I-d) and (I-k)
to (I-n) and the residues of the formulae (I-e) to (I-j) are
optionally substituted by one or more radicals selected from the
group consisting of hydroxy, C.sub.1-C.sub.30 alkyl,
C.sub.1-C.sub.30 alkyloxy, C.sub.2-C.sub.30 alkenyl,
C.sub.2-C.sub.30 alkenyloxy, C.sub.3-C.sub.12 cycloalkyl
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl;
C.sub.3-C.sub.12 cycloalkyloxy unsubstituted or substituted by 1, 2
or 3 C.sub.1-C.sub.4 alkyl; C.sub.6-C.sub.18 aryl, C.sub.6-C.sub.18
aryloxy, C.sub.2-C.sub.30carboxylate, C.sub.2-C.sub.30 carboxamide,
C.sub.2-C.sub.30 acyloxy, C.sub.1-C.sub.30 acyl, C.sub.1-C.sub.30
sulfonyl, --S--Z.sub.100, --S(O).sub.2(N(Z.sub.101).sub.2),
--N(Z.sub.102).sub.2, --F, --Cl, --Br, --NO.sub.2 or --COOH;
[0088] Z.sub.100, Z.sub.101, Z.sub.102 and Z.sub.1 independently of
one another are hydrogen, C.sub.1-C.sub.18 alkyl, C.sub.3-C.sub.18
alkenyl, C.sub.2-C.sub.12 cycloalkyl which is unsubstituted or
substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; phenyl which is
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; or
C.sub.7-C.sub.9 phenylalkyl which is unsubstituted or substituted
on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; and
[0089] when n is 2, Z is in particular a group of the formula
(II-a), (II-b), (II-c) or (II-d),
##STR00015##
[0090] the aromatic rings of the formulae (II-a) to (II-c) are
optionally substituted by one or more radicals selected from the
group consisting of hydroxy, C.sub.1-C.sub.30 alkyl,
C.sub.1-C.sub.30 alkyloxy, C.sub.2-C.sub.30 alkenyl,
C.sub.2-C.sub.30 alkenyloxy, C.sub.3-C.sub.12 cycloalkyl
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl;
C.sub.3-C.sub.12 cycloalkyloxy unsubstituted or substituted by 1, 2
or 3 C.sub.1-C.sub.4 alkyl; C.sub.6-C.sub.18 aryl, C.sub.6-C.sub.18
aryloxy, C.sub.2-C.sub.30 carboxylate, C.sub.2-C.sub.30
carboxamide, C.sub.2-C.sub.30 acyloxy, C.sub.1-C.sub.30 acyl,
C.sub.1-C.sub.30 sulfonyl, --S--Z.sub.100,
--S(O).sub.2(N(Z.sub.101).sub.2), --N(Z.sub.102).sub.2, --F, --Cl,
--Br, --NO.sub.2 or --COOH;
[0091] Z.sub.2 is >C.dbd.O, --O--, --S--, >N--R.sub.1,
>S.dbd.O or --S(O).sub.2--, C.sub.3-C.sub.30 diacyl,
C.sub.3-C.sub.30 di(acyloxy), C.sub.3-C.sub.45 dicarboxylate,
C.sub.3-C.sub.45 di(carboxamide), diamine or diamide;
[0092] Z.sub.3 and Z.sub.4 independently of one another are
>C.dbd.O, --O--, --S--, >N--R.sub.2, >S.dbd.O or
--S(O).sub.2--;
[0093] R.sub.1 and R.sub.2 independently of one another are
hydrogen, C.sub.1-C.sub.18 alkyl, C.sub.3-C.sub.18 alkenyl,
C.sub.3-C.sub.12 cycloalkyl which is unsubstituted or substituted
by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; phenyl which is unsubstituted
or substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; or
C.sub.7-C.sub.9 phenylalkyl which is unsubstituted or substituted
on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; when n is 4, Z is
a group of the formula (III-a)
##STR00016##
[0094] Examples of alkyl having up to 30 carbon atoms are methyl,
ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,
2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,
1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,
1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,
2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl,
nonyl, decyl, undecyl, 1-methylundecyl, dodecyl,
1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, octadecyl and eicosyl. In general, C.sub.1
-C.sub.20 alkyl, in particular C.sub.4-C.sub.20 alkyl or
C.sub.6-C.sub.20 alkyl is preferred. Z.sub.1, R.sub.1 and R.sub.2
independently of one another are e.g. C.sub.1-C.sub.4 alkyl.
[0095] Examples of C.sub.1-C.sub.30 alkyloxy are methoxy, ethoxy,
propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy,
2-ethylbutoxy, n-pentyloxy, isopentyloxy, 1-methylpentyloxy,
1,3-dimethylbutyloxy, n-hexyloxy, 1-methylhexyloxy, n-heptyloxy,
isoheptyloxy, 1,1,3,3-tetramethylbutyloxy, 1-methylheptyloxy,
3-methylheptyloxy, n-octyloxy, 2-ethylhexyloxy,
1,1,3-trimethylhexyloxy, 1,1,3,3-tetramethylpentyloxy, nonyloxy,
decyloxy, undecyloxy, 1-methylundecyloxy, dodecyloxy,
1,1,3,3,5,5-hexamethylhexyloxy, tridecyloxy, tetradecyloxy,
pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy and
eicosyloxy. C.sub.1-C.sub.20 alkyloxy is preferred.
[0096] Examples of alkenyl having up to 30 carbon atoms are allyl,
2-methallyl, butenyl, pentenyl, hexenyl and oleyl. The carbon atom
in position 1 is preferably saturated. C.sub.3-C.sub.18 alkenyl is
particularly preferred.
[0097] Examples of C.sub.2-C.sub.30 alkenyloxy are allyloxy,
2-methallyloxy, butenyloxy, pentenyloxy, hexenyloxy and oleyloxy.
C.sub.3-C.sub.18 alkenyloxy is particularly preferred.
[0098] Examples of C.sub.3-C.sub.12cycloalkyl unsubstituted or
substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl are cyclopentyl,
cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl and
2-methylcyclohexyl. C.sub.5-C.sub.6 cycloalkyl unsubstituted or
substituted by methyl are preferred.
[0099] Examples of C.sub.3-C.sub.12 cycloalkyloxy unsubstituted or
substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl are cyclopentyloxy,
cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclododecyloxy and
2-methylcyclohexyloxy. C.sub.5-C.sub.6cycloalkyloxy unsubstituted
or substituted by methyl are preferred.
[0100] Examples of C.sub.5-C.sub.12 cycloalkenyl unsubstituted or
substituted by 1, 2 or 3 C.sub.1-C.sub.4alkyl are cyclohexenyl and
methylcyclohexenyl.
[0101] Examples of C.sub.6-C.sub.18 aryl are phenyl and naphthyl
which may optionally be substituted. Unsubstituted or substituted
phenyl is preferred.
[0102] Examples of phenyl substituted by 1, 2 or 3 C.sub.1-C.sub.4
alkyl are 4-methylphenyl, 2-ethylphenyl, 4-ethylphenyl,
4-isopropylphenyl, 4-tert-butylphenyl, 4-sec-butylphenyl,
4-isobutylphenyl, 3,5-dimethylphenyl, 3,4-dimethylphenyl,
2,4-dimethylphenyl, 2,6-diethylphenyl, 2-ethyl-6-methylphenyl and
2,6-diisopropylphenyl.
[0103] Examples of C.sub.6-C.sub.18 aryloxy are phenyloxy and
naphthyloxy which may optionally be substituted. Phenyloxy
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl is
preferred. 4-methylphenyloxy, 2-ethylphenyloxy, 4-ethylphenyloxy,
4-isopropylphenyloxy, 4-tert-butylphenyloxy, 4-sec-butylphenyloxy,
4-isobutylphenyloxy, 3,5-dimethylphenyloxy, 3,4-dimethylphenyloxy,
2,4-dimethylphenyloxy, 2,6-diethylphenyloxy,
2-ethyl-6-methylphenyloxy and 2,6-diisopropylphenyloxy are
particularly preferred.
[0104] An example of diphenylmethyl substituted on the phenyl by 1,
2 or 3 C.sub.1-C.sub.4 alkyl is di[methylphenyl]methyl.
[0105] An examples of triphenylmethyl substituted on the phenyl by
1, 2 or 3 C.sub.1-C.sub.4 alkyl is tris[methylphenyl]methyl.
[0106] Examples of C.sub.7-C.sub.9 phenylalkyl unsubstituted or
substituted on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl are
benzyl, 2-phenylethyl, methylbenzyl, dimethylbenzyl,
trimethylbenzyl and tert-butylbenzyl.
[0107] Examples of acyl having up to 30 carbon atoms are
C.sub.2-C.sub.30 alkanoyl, C.sub.3-C.sub.30 alkenoyl and
unsubstituted or substituted benzoyl. C.sub.2-C.sub.20alkanoyl,
C.sub.2-C.sub.20 alkenoyl and substituted benzoyl are preferred.
Acetyl, propionyl, butyryl, pentanoyl, hexanoyl, octanoyl, benzoyl,
acryloyl and crotonoyl are more specific examples. A group of the
formula
##STR00017##
[0108] as well as C.sub.2-C.sub.20 alkanoyl and C.sub.3-C.sub.20
alkenoyl are particularly preferred.
[0109] A preferred example of C.sub.1-C.sub.30 sulfonyl is the
group
##STR00018##
[0110] wherein A.sub.1 is C.sub.1-C.sub.30 alkyl, C.sub.3-C.sub.30
alkenyl, C.sub.3-C.sub.12cycloalkyl which is unsubstituted or
substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; phenyl
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.20 alkyl;
or C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted
on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4 alkyl. A particularly
preferred radical is
##STR00019##
[0111] which may optionally be substituted. Further examples of
sulfonyl are
##STR00020##
[0112] Examples of a bicyclic or tricyclic hydrocarbyl having 6 to
10 carbon atoms are
##STR00021##
[0113] A preferred example of C.sub.2-C.sub.30 carboxylate is the
group
##STR00022##
[0114] wherein A.sub.2 is C.sub.1-C.sub.29 alkyl, C.sub.3-C.sub.18
alkenyl, C.sub.3-C.sub.12 cycloalkyl which is unsubstituted or
substituted by 1, 2 or 3 C.sub.1-C.sub.4alkyl; phenyl unsubstituted
or substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl; or
C.sub.7-C.sub.9 phenylalkyl which is unsubstituted or substituted
on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4 alkyl.
##STR00023##
[0115] is particularly preferred.
[0116] A preferred example of C.sub.2-C.sub.30 carboxamide is the
group
##STR00024##
[0117] wherein A'.sub.2 has one of the definitions of A.sub.2
##STR00025##
[0118] is particularly preferred.
[0119] Examples of C.sub.2-C.sub.30 acyloxy are C.sub.2-C.sub.20
alkanoyloxy, C.sub.3-C.sub.20 alkenoyloxy and substituted
benzoyloxy are preferred. Acetyloxy, propionyloxy, butyryloxy,
pentanoyloxy, hexanoyloxy, octanoyloxy, benzoyloxy, acryloyloxy and
crotonoyloxy are more specific examples. C.sub.2-C.sub.20
alkanoyloxy, C.sub.3-C.sub.20 alkenoyloxy and benzoyloxy are
particularly preferred.
[0120] A preferred example of C.sub.3-C.sub.30 diacyl is the
group
##STR00026##
[0121] wherein A.sub.3 is C.sub.2-C.sub.20 alkylene,
C.sub.2-C.sub.20 alkylene interrupted by oxygen, sulphur or
>N--R.sub.3 with R.sub.3 having one of the meanings of R.sub.1;
C.sub.2-C.sub.12 alkenylene, C.sub.2-C.sub.12 alkynylene,
C.sub.5-C.sub.12 cycloalkylene, C.sub.5-C.sub.12
cycloalkylene-(C.sub.1-C.sub.4 alkylene)-C.sub.5-C.sub.12
cycloalkylene, C.sub.1-C.sub.4 alkylene-(C.sub.5-C.sub.12
cycloalkylene)-C.sub.1-C.sub.4 alkylene, phenylene,
phenylene-(C.sub.1-C.sub.4alkylene)-phenylene or
C.sub.1-C.sub.4alkylene-phenylene-C.sub.1-C.sub.4alkylene.
[0122] A preferred example of C.sub.3-C.sub.30 di(acyloxy) is the
group
##STR00027##
[0123] wherein A.sub.4 has one of the definitions of A.sub.3.
[0124] A preferred example of C.sub.3-C.sub.45 dicarboxylate is the
group
##STR00028##
[0125] wherein A5 has one of the definitions of A3. A further
preferred example is
##STR00029##
[0126] A preferred example of C.sub.3-C.sub.45 di(carboxamide) is
the group
##STR00030##
[0127] wherein A'5 has one of the definitions of A3.
[0128] A preferred example of diamine is the group
##STR00031##
[0129] wherein R.sub.4 and R.sub.5 independently of one another
have one of the meanings of R.sub.1 and A.sub.6 has one of the
meanings of A.sub.3.
[0130] A preferred example of diamide is the group
##STR00032##
[0131] wherein R6 and R.sub.7 independently of one another have one
of the definitions of R.sub.1 and A.sub.7 has one of the
definitions of A3.
[0132] Examples of alkylene having up to 20 carbon atoms are
ethylene, propylene, trimethylene, tetramethylene, pentamethylene,
hexamethylene, octamethylene, decamethylene and
dodecamethylene.
[0133] Examples of alkylene having up to 20 carbon atoms and being
interrupted by oxygen, sulphur or >N--R.sub.3 are
3-oxapentane-1,5-diyl, 4-oxaheptane-1,7-diyl,
3,6-dioxaoctane-1,8-diyl, 4,7-dioxadecane-1,10-diyl,
4,9-dioxadodecane-1,12-diyl, 3,6,9-trioxaundecane-1,11-diyl,
4,7,10-trioxatridecane-1,13-diyl, 3-thiapentane-1,5-diyl,
4-thiaheptane-1,7-diyl, 3,6-dithiaoctane-1,8-diyl,
4,7-dithiadecane-1,10-diyl, 4, 9-dithiadodecane-1,12-diyl,
3,6,9-trithiaundecane-1,11-diyl, 4,7, 10-trithiatridecane-1,13-diyl
and
--CH.sub.2CH.sub.2CH.sub.2--N(R.sub.3)--CH.sub.2CH.sub.2--N(R.sub.3)--CH.-
sub.2CH.sub.2CH.sub.2--, in particular
--CH.sub.2CH.sub.2CH.sub.2--N(CH.sub.3)--CH.sub.2CH.sub.2--N(CH.sub.3)--C-
H.sub.2CH.sub.2CH.sub.2--.
[0134] An example of C.sub.2-C.sub.12 alkenylene is
3-hexenylene.
[0135] An example of C.sub.2-C.sub.12 alkynylene is
[0136] --CH.sub.2CH.sub.2--C.ident.C--CH.sub.2CH.sub.2--
[0137] C.sub.6-C.sub.12 alkynylene is preferred.
[0138] An example of C.sub.5-C.sub.12 cycloalkylene is
cyclohexylene.
[0139] Examples of C.sub.5-C.sub.12 cycloalkylene-(C.sub.1-C.sub.4
alkylene)-C.sub.5-C.sub.12 cycloalkylene are
methylenedicyclo-hexylene and isopropylidenedicyclohexylene.
[0140] An example of C.sub.1-C.sub.4 alkylene-(C.sub.5-C.sub.12
cycloalkylene)-C.sub.1-C.sub.4 alkylene is
cyclohexylenedimethylene.
[0141] An example of phenylene-(C.sub.1-C.sub.4 alkylene)-phenylene
is methylenediphenylene.
[0142] An example of C.sub.1-C.sub.4
alkylene-phenylene-C.sub.1-C.sub.4 alkylene is
phenylenedimethylene.
[0143] Preferred examples of the radical X are >C.dbd.O,
>S(O).sub.2, >CH.sub.2, >C(CH.sub.3).sub.2 and
>C(phenyl).sub.2.
[0144] X as >C.dbd.O is particularly preferred.
[0145] n is preferably 1 or 2,
[0146] For n=1, Z is preferably a group of the formula (I-a) or
(I-d), and for n=2, Z is preferably a group of the formula (II-a)
or (II-c).
[0147] A preferred example of the group (I-a) is the residue of the
formula (I-a-1).
##STR00033##
[0148] Particularly preferred embodiments of the present invention
are:
[0149] 1) A polymer article as defined above, wherein Y is hydrogen
and
[0150] when n is 1, Z is a group of the formula (I-b), (I-c),
(I-d), (I-j, (I-k), (I-l), (I-n) or (I-m), and
[0151] when n is 2, Z is a group of the formula (II-a), (II-b),
(II-c) or (II-d).
[0152] 2) A polymer article as defined above, wherein
[0153] when n is 1, Z is a group of the formula (I-a) unsubstituted
or substituted by C.sub.2-C.sub.30 carboxylate or C.sub.2-C.sub.30
carboxamide; and
[0154] when n is 2, Z is a group of the formula (II-a) or
(II-c).
[0155] 3) A polymer article as defined above, wherein
[0156] when n is 1, Z is a group of the formula (I-a) substituted
on the aromatic ring by --COOH, an C.sub.8-C.sub.22
alkylcarboxylate of the formula
##STR00034##
[0157] or an C.sub.8-C.sub.22 alkylcarboxamide of the formula
##STR00035##
[0158] or a group of the formula (I-d); and
[0159] when n is 2, Z is a group of the formula (II-c) wherein
Z.sub.2 is a dicarboxylate of the formula
##STR00036##
[0160] or a di(carboxamide) of the formula
##STR00037##
[0161] 4) A polymer article as defined above, wherein Y is
C.sub.1-C.sub.30 alkyl, C.sub.7-C.sub.9 phenylalkyl unsubstituted
or substituted on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4 alkyl;
triphenylmethyl unsubstituted or substituted on the phenyl by 1, 2
or 3 C.sub.1-C.sub.4 alkyl; C.sub.2-C.sub.30 acyl, --COOY.sub.0,
C.sub.1-C.sub.30 sulfonyl or --Si(Y.sub.1).sub.3; and Y.sub.0 and
Y.sub.1 are C.sub.1-C.sub.18 alkyl or phenyl which is unsubstituted
or substituted by 1, 2 or 3 C.sub.1-C.sub.4 alkyl.
[0162] 5) A polymer article as defined above, wherein n is 1 or 2,
and
[0163] when n is 1, Z is a group of the formula (I-a) or (I-d), the
aromatic rings of the formula (I-a) or (I-d) are optionally
substituted by C.sub.2-C.sub.30 carboxylate or --COOH;
[0164] when n is 2, Z is a group of the formula (II-a) or (II-c),
and
[0165] Z.sub.2 is >C.dbd.O or C.sub.3-C.sub.45
dicarboxylate.
[0166] 6) A polymer article as defined above, wherein
[0167] n is 1 or 2;
[0168] Y is C.sub.1-C.sub.30 alkyl, triphenylmethyl, benzyl,
C.sub.2-C.sub.30 alkanoyl,
##STR00038##
[0169] --COOY.sub.0 with Y.sub.0 being C.sub.1-C.sub.18 alkyl;
tosyl or tert-butyldiphenylsilanyl, and when n is 2, Y is
additionally hydrogen;
[0170] when n is 1, Z is a group of the formula
##STR00039##
[0171] Z.sub.0 is COOH or --COO-(C.sub.1-C.sub.20 alkyl);
[0172] when n is 2, Z is a group of the formula
##STR00040##
[0173] 7) A polymer article as defined above, wherein component (B)
is a compound of the formula
##STR00041##
[0174] The synthesis of the cited examples is best carried out as
described in the following Examples. The examples illustrate the
invention in greater detail. All percentages and parts are by
weight, unless stated otherwise.
[0175] Incorporation of the various additives is best performed in
a thermal compounding step, mixing thoroughly the oxidation
additives and optional additives, followed by an extrusion of the
physical blend at elevated temperature. Typically an extruder with
suitable screw configuration is used for this step. The additives
can also be added in the form of a preconfectioned masterbatch
produced in a different manner. For the production of the desired
article any appropriate machine can be used, depending on the final
form of the article, for example a blow extruder in the case of
films, a cast extrusion machine in the case of sheets or an
injection-molding machine.
[0176] Oxidant Additives: Accessibility of the starting
materials:
[0177] Starting materials for the cited examples 1-6 are
commercially available compounds, for example
[0178] N-hydroxy phthalimide
[0179] Pyromellitic dianhydride
[0180] Phthalic anhydride
[0181] N-dodecylbenzene
[0182] Hydroxylamine hydrochloride
[0183] Manganese stearate
[0184] Poly-alpha-pinene
[0185] Poly-beta-pinene
[0186] Poly limonene
[0187] Other base nuclei that can be used are:
[0188] Trimellitic anhydride anhydride
[0189] N-hydroxyl,8-phthalimide
[0190] Perylene tetracarboxylic acid
[0191] Saccharin
[0192] Modifications were carried out with commercially available
compounds such as stearoyl chloride
[0193] p-toluenesulfonyl chloride
[0194] trityl chloride
TABLE-US-00003 Example 1 2 Structure ##STR00042## ##STR00043##
Melting point 285-288.degree. C. 209-216.degree. C. MW (g/mol)
213.19 379.42 Data of 210.degree. C.: 0.34% 210.degree. C.: 0.23%
thermogravimetric 260.degree. C.: 2.92% 260.degree. C.: 1.35%
analysis/weight loss 300.degree. C.: 21.41% 300.degree. C.: 11.11%
Example 3 4 Structure ##STR00044## ##STR00045## Melting point
157-164.degree. C. 232-239.degree. C. MW (g/mol) 317.32 367.38 Data
of 210.degree. C.: 0.80% 210.degree. C.: 0.18% thermogravimetric
260.degree. C.: 3.92% 260.degree. C.: 0.24% analysis/weight loss
300.degree. C.: 59.62% 300.degree. C.: 28.86% Example 5 6 Structure
##STR00046## ##STR00047## Melting point 76-81.degree. C.
159-166.degree. C. MW (g/mol) 479.67 276.24 Data of 210.degree. C.:
0.01% 210.degree. C.: 1.24% thermogravimetric 260.degree. C.: 2.24%
260.degree. C.: 3.23% analysis/weight loss 300.degree. C.: 19.68%
300.degree. C.: 7.81% Example 7 8 Structure ##STR00048##
##STR00049## Melting point 274-277.degree. C. 94-98.degree. C. MW
(g/mol) 455.52 Mn: 4043; Mw: 7432 Data of 210.degree. C.: 0.11%
210.degree. C.: 1.28% thermogravimetric 260.degree. C.: 2.16%
260.degree. C.: 6.19% analysis/weight loss 300.degree. C.: 13.86%
300.degree. C.: 43.39% ##STR00050##
[0195] Compounds of the following Examples 1, 3 and 5 have been
prepared following procedures disclosed in the WO 2007/028731
A1
EXAMPLE 2
di phenyloxy-1,8-naphthalimide
##STR00051##
[0197] A four-necked round-bottom flask equipped with a mechanical
stirrer, thermocouple, dropping funnel and condenser is
successively charged with 200 ml of DMA, 17.8 g of triethylamine
and 24.9 g of diphenylchloromethane and 25 g of
N-hydroxy-1,8-naphthalimide. The stirred mixture is then heated up
at 90.degree. C. for 8 hours. The reaction mixture is then cooled
down at room temperature and the precipitate is separated by
filtering off the solution, washed with water several times and
dried in oven under vacuum at 100.degree. C. The product is
obtained as a white solid.
EXAMPLE 4
N-p-toluene-4-sulfonyloxynaphthalimide
##STR00052##
[0199] A four-necked round-bottom flask equipped with a mechanical
stirrer, thermocouple, dropping funnel and condenser is
successively charged with 200 ml of THF, 17.8 g of triethylamine
and 25 g of N-hydroxy-1,8-naphthalimide. To this stirred mixture is
then slowly added, at room temperature, 23.5 g of p-toluenesulfonyl
chloride; the reaction is then heated at reflux for 4 hours. The
reaction mixture is then cooled down at room temperature; the
precipitate is separated by filtering off the solution, washed with
water several times and dried in oven under vacuum at 100.degree.
C. The product is obtained as a white solid.
EXAMPLE 6
Acrylox-1,8-naphthalimide
##STR00053##
[0201] A four-necked round-bottom flask equipped with a mechanical
stirrer, thermocouple, dropping funnel and condenser is
successively charged with 500 ml of THF, 11.44 g of triethylamine
and 20 g of N-hydroxy-1,8-naphthalimide. 9.34 g of Acryloyl
chloride are slowly added to the mixture and the reaction is
stirred at room temperature for 16 hours. The white precipitate is
filtered off and the solvent removed under reduce pressure to give
an orange solid which is crystallized from 200 mL of isopropanol as
a white solid and dried in oven under vacuum at 100.degree. C.
EXAMPLE 7
tri-(trityloxy)-1,8-naphthalimide
##STR00054##
[0203] A four-necked round-bottom flask equipped with a mechanical
stirrer, thermocouple, dropping funnel and condenser is
successively charged with 25.0 g N-hydroxy-1,8-naphthalimide, 17.76
g of triethylamine in 200 ml of DMF. 32.69 g of Trityl chloride are
slowly added to the mixture and the reaction is stirred at room
temperature for 16 hours. The white precipitate is filtered and
washed with H.sub.2O, hexane, THF and finally dried in oven under
vacuum at 100.degree. C.
EXAMPLE 8
##STR00055##
[0205] A four-necked round-bottom flask equipped with a mechanical
stirrer, thermocouple, dropping funnel and condenser is
successively charged with 20.0 g of compound 6, 63.86 g of butyl
methacrylate and 4.0 g of AIBN in 400 ml of THF. The mixture is
heated at reflux for 4 hours. The solvent is then removed and the
solid dissolved in 400 ml of CH.sub.2Cl.sub.2, washed with H.sub.2O
and the organic phase dried over Na.sub.2SO.sub.4. The solvent is
removed to give a light yellow solid which is washed with 100 ml of
cold MeOH and finally dried in oven under vacuum at 90.degree.
C.
[0206] Riblene GP20.RTM. low density polyethylene has been obtained
from Polimeri Europa; Dercolyte is a poly terpene product obtain
from Les Derives Resiniques & Terpeniques; Manganese Stearate,
Mn(C.sub.18H.sub.35O.sub.2).sub.x, has been purchased from Shepherd
Chemical Company and Shelfplus O.sub.2 2400.RTM. has been obtain
from ALBIS.
[0207] Comparative Sample 1:
[0208] Shelfplus O.sub.2 2400.RTM. was mixed in a 1:1 ratio with
low density polyethylene, Riblene.RTM. so that the final Iron
concentration was 5.0% by weight. Compounds were prepared with an
OMC pilot double screw extruder (model EBV 19/25, with a 19 mm
screw diameter and 1:25 ratio), and 50 micron-thick films were
prepared using Collin Cast Flat-die Extruder model 30.times.25 L/D
(30 mm screw diameter, 1:25 diameter/length ratio).
[0209] Comparative Sample 2:
[0210] 2.0% of polyterpenic resin Dercolyte.RTM. was mixed with low
density polyethylene, Riblene.RTM.. Compounds and Film were
prepared as described in Comparative Sample 1.
[0211] Comparative Sample 3:
[0212] 0.2% of Manganese Stearate was mixed with low density
polyethylene, Riblene.RTM.. Compounds and Film were prepared as
described in Comparative Sample 1.
[0213] Inventive Sample 4:
[0214] 2.0% of polyterpenic resin Dercolyte.RTM., 0.2% of Manganese
Stearate and 0.2% of Example 2 were mixed with low density
polyethylene, Riblene.RTM.. Compounds and Film were prepared as
described in Comparative Sample 1.
[0215] Inventive Sample 5:
[0216] 2.0% of polyterpenic resin Dercolyte.RTM., 0.2% of Manganese
Stearate and 0.2% of Example 3 were mixed with low density
polyethylene, Riblene.RTM.. Compounds and Film were prepared as
described in Comparative Sample 1.
[0217] Inventive Sample 6:
[0218] 2.0% of polyterpenic resin Dercolyte.RTM., 0.2% of Manganese
Stearate and 0.2% of Example 4 were mixed with low density
polyethylene, Riblene.RTM.. Compounds and Film were prepared as
described in Comparative Sample 1.
[0219] Inventive Sample 7:
[0220] 2.0% of polyterpenic resin Dercolyte.RTM., 0.2% of Manganese
Stearate and 0.2% of Example 5 were mixed with low density
polyethylene, Riblene. Compounds and film were prepared as
described in Comparative Sample 1.
[0221] Inventive Sample 8:
[0222] 2.0% of polyterpenic resin Dercolyte.RTM., 0.2% of Manganese
Stearate and 0.2% of Example 7 were mixed with low density
polyethylene, Riblene.RTM.. Compounds and Film were prepared as
described in Comparative Sample 1.
[0223] Inventive Sample 9:
[0224] 2.0% of polyterpenic resin Dercolyte.RTM., 0.2% of Manganese
Stearate and 0.45% of Example 8 were mixed with low density
polyethylene, Riblene.RTM.. Compounds and Film were prepared as
described in Comparative Sample 1.
[0225] Inventive Sample 10:
[0226] 2.0% of polyterpenic resin Dercolyte.RTM. and 0.2% of
Manganese Stearate were mixed with low density polyethylene,
Riblene.RTM.. Compounds and Film were prepared as described in
Comparative Sample 1.
[0227] Several aliquots of film for each sample were then exposed
to air (20.7% O.sub.2) in 500 ml sealed flasks provided with a
septum that allowed portions of the inside atmosphere to be drawn
for analysis at several intervals using a syringe. Oxygen
concentration measures were carried out using a Mocon Pac Check 450
head space analyzer over 28 days. The actual iron concentration in
Comparative Sample 1 was measured by ICP -OES (Inductively Coupled
Plasma--Optical Emission Spectrometer, Perkin Elmer Optima Series
4200DV). The results in terms of ml O.sub.2/g of active scavenger
are given in Table 1.
TABLE-US-00004 TABLE 1 Averaged oxygen scavenger activity (ml
O.sub.2/g Scavenger) for six different LDPE film measured after 28
days. In case of Comparative Sample 1*: g of active scavenger = g.
of iron in the film; in all the other cases: g. of active scavenger
= g. of Dercolyte + g. of metal complex + g. of nitroxyl molecule.
ml O.sub.2/g. Iron after 28 Days Comparative Sample 1* 36
Comparative Sample 2 No O.sub.2 uptake detectable Comparative
Sample 3 No O.sub.2 uptake detectable Inventive Sample 4 92
Inventive Sample 5 83 Inventive Sample 6 72 Inventive Sample 7 97
Inventive Sample 8 53 Inventive Sample 9 88 Inventive Sample 10
69
[0228] Description of Oxygen uptake Method:
[0229] Film thickness is measured and 4.0 grams of film are
weighted. The extruded film is folded and placed in a clean 500 ml
sealed glass container. A vial containing 15 ml of deionized water
is added to produce 100% relative humidity inside the glass
container (only for Comparative Sample 1).
[0230] The oxygen content in the ambient air on day 0 (i.e. equal
to the initial oxygen content in the sealed glass container) is
tested and recorded using a Mocon Oxygen Analyzer.
[0231] The glass containers with test films and water vials are
stored at 22.degree. C. (generally, room temperature) for 28
days.
[0232] The oxygen content in the sealed glass containers using a
Mocon Oxygen Analyzer on day 28 are tested and recorded.
[0233] Based on the measured oxygen concentration that is left in
the sealed glass container the volume of oxygen absorbed per gram
of Scavenger has been calculated using the formula:
Oxygen absorbed (ml/g)={(% O.sub.2).sub.i-(%
O.sub.2).sub.f}*0.01*V.sub.j/(W.sub.F*W.sub.S/W.sub.B)
[0234] where: [0235] (% O.sub.2).sub.i Initial oxygen concentration
in the sealed glass container (%) [0236] (% O.sub.2).sub.f Oxygen
concentration in the sealed glass container at day of test (%)
[0237] 0.01: Conversion factor [0238] V.sub.j: Free air volume of
the sealed glass container (ml) (total volume of the sealed glass
container less space occupied by vial and film, typically 440 ml)
[0239] W.sub.F: Weight of film placed into the glass container
(typically 4.0 g) [0240] W.sub.S: Weight of Oxygen Scavenger used
to make blend (g) [0241] W.sub.B: Total weight of blend (g)
[0242] The invention can be applied in all areas of packaging where
oxygen scavenger activity is desired.
[0243] For example, the polymer article may be used to manufacture
plastic films, sheets, laminates, bags, bottles, styrofoam cups,
utensils, blister packages, boxes, package wrappings. The articles
may be manufactured by any process available to those of ordinary
skill in the art including, but not limited to, extrusion,
extrusion blowing, film casting, film blowing, calendering,
injection molding, blow molding, compression molding,
thermoforming, spinning, blow extrusion and rotational casting. In
particular, this is of interest in the area of modify atomsphere
(002, N.sub.2) food packaging. The rate of the oxygen uptake can
simply be adjusted by changing the concentration of the additives
i.e. if higher oxygen scavenger performance is desired, then higher
amount of additives is added.
* * * * *