U.S. patent application number 11/232513 was filed with the patent office on 2006-03-16 for romp with alkoxy ether groups.
Invention is credited to Piero Piccinelli, Manuele Vitali, Alessandro Zedda.
Application Number | 20060058476 11/232513 |
Document ID | / |
Family ID | 8183786 |
Filed Date | 2006-03-16 |
United States Patent
Application |
20060058476 |
Kind Code |
A1 |
Piccinelli; Piero ; et
al. |
March 16, 2006 |
ROMP with alkoxy ether groups
Abstract
The invention relates to metathesis oligomers wherein one or
more alkoxy ether groups are attached to the oligomer moiety. Also
disclosed is a polymerisable composition comprising a catalytically
effective amount of a penta- or hexavalent ruthenium or osmium
carbene catalyst, the process for preparing the metathesis polymer
by applying the reaction conditions of Ring Opening Metathesis
Polymerisation (=ROMP) to the polymerisable composition; and
various technical applications of the metathesis oligomers as
antifog agents.
Inventors: |
Piccinelli; Piero; (Sasso
Marconi, IT) ; Vitali; Manuele; (Bologna, IT)
; Zedda; Alessandro; (Basel, CH) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION;PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
8183786 |
Appl. No.: |
11/232513 |
Filed: |
September 22, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10093983 |
Mar 8, 2002 |
|
|
|
11232513 |
Sep 22, 2005 |
|
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Current U.S.
Class: |
526/171 ;
524/366; 568/670 |
Current CPC
Class: |
C08L 53/00 20130101;
C08F 293/005 20130101; C08L 53/00 20130101; C08L 53/00 20130101;
C08L 2666/02 20130101; C08F 293/00 20130101; C08L 2666/04
20130101 |
Class at
Publication: |
526/171 ;
524/366; 568/670 |
International
Class: |
C08K 5/06 20060101
C08K005/06; C09J 7/02 20060101 C09J007/02; C07C 43/18 20060101
C07C043/18 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 12, 2001 |
EP |
01810246.7 |
Claims
1. A compound of the formula
A-[X-(Y-Z).sub.p].sub.m[X'(Y'-Z').sub.q].sub.nB-Z'' (1), wherein
one of m and n represents zero, one or a numeral greater than one
and the other one represents one or a numeral greater than one,
with the proviso that the sum of m and n is at least two; p and q
independently of one another represent zero, one or a numeral
greater than one and the other one represents one or a numeral
greater than one; A and B represent chain terminal groups from the
chain transfer agent A-B; X and X' independently of one another
represent unsaturated or hydrogenated repeating units from
cycloolefins polymerised by metathesis; Y and Y' represent
identical or different bivalent groups; and Z, Z' and Z''
independently of one another represent alkoxy ether groups selected
from the group consisting of
hydroxy-C.sub.2-C.sub.3alkoxy-poly-C.sub.2-C.sub.3alkoxy and
C.sub.1-C.sub.4alkoxy-poly-C.sub.2-C.sub.3alkoxy; or Z, Z' and Z''
independently of one another represent alkoxy ether groups selected
from the group consisting of dihydroxy-C.sub.3-C.sub.7alkoxy and
dihydroxy-C.sub.2-C.sub.3alkoxy-poly-C.sub.2-C.sub.3alkoxy, wherein
hydroxy is etherified by another group A-X''-B, wherein A-B
represent chain terminal groups from the chain transfer agent A-B
and X'' represents unsaturated or hydrogenated repeating units from
cycloolefins polymerised by metathesis.
2. A compound (I) according to claim 1, wherein X and X'
independently of one another represent an unsaturated or
hydrogenated repeating unit from cycloolefins polymerised by
metathesis selected from the group consisting of cyclopropene,
cyclobutene, cyclopentene, cycloheptene, cyclooctene,
cyclopentadiene, dicyclopentadiene, cyclohexadiene,
cycloheptadiene, cyclooctadiene, norbornadiene, norbornene and
norbornene derivatives; and A, B, Y, Y', Z, Z', Z'', p, q, m and n
are as defined in claim 1.
3. A compound (I) according to claim 1, wherein one of m and n
represents a numeral from 2 to 20; and the other one represents
zero; and A, B, X, X', Y, Y', Y'', Z, Z', Z'', p and q are as
defined in claim 1.
4. A compound (I) according to claim 1, wherein Z, Z' and Z''
independently of one another represent alkoxy ether groups selected
from the group consisting of 2-hydroxyethoxy-polyethoxy,
2-C.sub.1-C.sub.4alkoxy-polyethoxy, 3-hydroxypropoxypoly-n-propoxy
and 3-C.sub.1-C.sub.4alkoxy-poly-n-propoxy; and A, B, X, X', Y, Y',
Y'', p, q, m and n are as defined in claim 1.
5. A compound (I) according to claim 1, wherein Z, Z' and Z''
independently of one another represent methoxy-polyethoxy,
polyethoxy, methoxy-poly-n-propoxy, and ethoxy-poly-n-propoxy; and
A, B, X, X', Y, Y', Y'', p, q, m and n are as defined in claim
1.
6. A compound (I) according to claim 1, wherein p and q represent
zero; one of m and n represents a numeral from 2 to 20 and the
other one represents zero; A and B represent chain terminal groups
from the chain transfer agent C.sub.3-C.sub.8alkene; X and X'
independently of one another represent an unsaturated or
hydrogenated repeating unit from cycloolefins polymerised by
metathesis selected from the group consisting of cyclopropene,
cyclobutene, cyclopentene, cycloheptene, cyclooctene,
cyclopentadiene, dicyclopentadiene, cyclohexadiene,
cycloheptadiene, cyclooctadiene, norbornadiene, norbornene and
norbornene derivatives; Y and Y' independently of one another
represent bivalent groups selected from the group consisting of
--C(.dbd.O)--, --O--C(.dbd.O)-- and C.sub.1-C.sub.8alkylene; and Z,
Z' and Z'' independently of one another represent an alkoxy ether
group selected from the group consisting of methoxy-polyethoxy,
polyethoxy, methoxy-poly-n-propoxy, and ethoxy-poly-n-propoxy.
7. A compound (I) according to claim 1, wherein p and q represent
zero; one of m and n represents a numeral from 2 to 20 and the
other one represents zero; A and B represent chain terminal groups
from the chain transfer agent C.sub.3-C.sub.8alkene; X and X'
independently of one another represent an unsaturated or
hydrogenated repeating unit from cycloolefins polymerised by
metathesis selected from the group consisting of cyclopentadiene,
dicyclopentadiene, norbornadiene, norbornene and norbornene
derivatives; and Z'' represents an alkoxy ether group selected from
the group consisting of methoxy-polyethoxy, polyethoxy,
methoxy-poly-n-propoxy, and ethoxy-poly-n-propoxy.
8. A compound according to claim 1 selected from the group
consisting of ##STR23## wherein m and a represent numerals from 5
to 20.
9-14. (canceled)
15. A method for increasing the antifog properties of polymers
which comprises incorporating within film polymer material a
compound according to claim 1.
16. A method according to claim 15, wherein the film material is a
greenhouse or food packaging film material.
Description
[0001] This is a continuation of U.S. application Ser. No.
10/093,983, filed Mar. 8, 2002, pending, which is incorporated by
reference.
[0002] The invention relates to compounds wherein one or more
alkoxy ether groups are attached to an oligomer moiety and to the
use of these compounds for preventing the fog formation from
humidity under polymer films.
[0003] The invention particularly relates to metathesis oligomers
wherein a surface active alkoxy ether group, particularly a
polyalkoxy ether group, is attached to the oligomer; a
polymerisable composition comprising a catalytically effective
amount of a penta- or hexavalent ruthenium or osmium carbene
catalyst; the process for preparing the metathesis polymer by
applying the reaction conditions of Ring Opening Metathesis
Polymerisation (=ROMP) to the polymerisable composition; and
various technical applications of the metathesis oligomers.
[0004] Films and foils for agricultural and horticultural
applications, so-called agricultural films, are used as covers for
greenhouse cultures or as protecting covers for open field
cultures, e.g. so-called under foil cultures or tunnel cultures,
depending on the size and the height of the plant. The atmosphere
under these films and foils is saturated with water vapour, which
evaporates from the soil or from the plants. The water vapour then
condenses to droplets on the inner surface of the films. This
reduces the intensity of the incident sunlight and increases the
risk of plant diseases. The reduction in light transmission slows
down the rate of plant growth; delays crop maturity and reduces the
crop yield per plant.
[0005] Another problem closely related to this one applies to
so-called food packaging films when food, e.g. meat products, are
packaged on trays and wrapped with a plastic film at room
temperature. When these packages are placed in a refrigerator at
around 4.degree. C., the air enclosed in the package is
oversaturated and the water condenses as water droplets onto the
film's surface.
[0006] The term fogging is used to describe the condensation of
water vapour on a plastic film's surface in the form of small,
discrete water droplets. Fogging results when an enclosed mass of
air containing water vapour cools to a temperature below its dew
point. The phenomenon is very much dependent upon the temperature
and relative humidity of the enclosed water vapour/air mixture, as
well as the temperature of the contact film.
[0007] To overcome these problems, polymer films are modified with
antifogging additives. The modified plastic films do not prevent
the formation of condensation per se. However, while water vapour
condenses on such films, antifogging additives migrate to the
surface of the film, causing the condensate to spread evenly over
the film's surface and run off instead of forming droplets, cf.
Plastics Additives Handbook, 5.sup.th Edition 2001, Hans Zweifel
Ed., HANSER (Hanser Publisher Munich, Hanser Gardner Publications,
Inc. Cincinnati) ISBN 3-446-21654-5, pages 609-626.
[0008] Representative antifogging additives are glycerol
monooleate, polyglycerol esters, sorbitan esters, ethoxylated
sorbitan esters, and nonylphenol ethoxylate or ethoxylated
alcohols. As representative state of the art U.S. Pat. No.
5,262,233 is cited, which discloses the incorporation of
polyethylene oxide alkyl ethers as non-ionic surfactants in
agricultural polymeric films.
[0009] Antifogging additives can be incorporated within the polymer
matrix as pure additives or as master batches or concentrates.
Typical antifogging additive concentrations range between 1 and 3%.
However, the additives have the undesirable property of migrating
to the surface of the film. In a mono-layer film, the antifogging
additives migrate in both directions, towards the inside of the
agricultural film where the antifogging effect is desirable, but
also to the outside of the film where it is unnecessary. On the
outside of the polymer film, antifogging additive is lost as it is
washed off by rain.
[0010] Surfactant molecules coatings have the undesirable property
of forming a weak attachment to polymeric films or foils,
particularly polyethylene films, and are washed away by the action
of heat and humidity. Therefore, there is a need for improved
polymer films, which resist fogging when they are exposed for a
longer period of time to conditions of higher temperatures and
humidity.
[0011] To overcome this problem, three layer films have been
developed and commercialised. The middle layer is about 50% of the
total film thickness, while the inside and outside layers is each
approximately 25% of the total film thickness. The inside layer
contains about 1% antifogging additive to provide immediate
antifogging effect after placing the film on the agricultural
field. The polymer film is typically a PE (=polyethylene)-EVA
(=ethylene vinyl acetate) copolymer with a low level of vinyl
acetate, e.g. 4 to 6%. In the middle layer is the bulk of the
antifogging additive, which provides the long-term fogging effect.
The concentration of the antifogging additive in this layer is
between 3 and 5%. The polymer used for this layer is a PE-EVA
copolymer with a high level of vinyl acetate, e.g. 14 to 18%. The
outside layer is a barrier layer based on PE. This layer contains
no or very little antifogging additive. When the antifogging
additive from the inside layer is consumed and washed off, some of
the antifogging additive in the middle layer migrates into the
inside layer. A large number of commercial products is available
from different suppliers under various trade names, e.g.
Glycolube.RTM. (Lonza, CH-Basel), Loxiol.RTM. (Henkel,
DE-Dusseldorf) or Armofog.RTM. (Akzo, NL-Amersfoort).
[0012] Three layer films improve the properties of agricultural
films to some degree, but do not overcome the problem that
surfactants materials are lost caused by washing off from the
films. Moreover, three layer films require the application of
difficult extrusion techniques by co-extrusion with different
polymer materials.
[0013] It has surprisingly been found out that the efficiency of
films and foils to resist fogging is increased if oligomers
obtained by ROMP containing surface-active alkoxy ether groups are
added to the polymers. The non-ionic alkoxy ether groups are
directly linked to the oligomer structure by chemical bonds, such
as ether or ester bonds.
[0014] Thermal ROMP of cycloolefins other than cyclohexene has
acquired great importance. This method requires appropriate
catalysts. Catalysts of particular interest for ROMP are so-called
metal carbenes, for example ruthenium and osmium complexes, bearing
the group .dbd.CR*R** (wherein one of R* and R** represents
hydrogen and the other represents phenyl, alkyl or alkenyl or both
represent alkyl or alkenyl) attached to the central metal atom [WO
93/20111; S. Kanaoka et al., Macromolecules 28:4707-4713 (1995); C.
Fraser et al., Polym. Prepr. 36:237-238 (1995); P. Schwab et al.,
Angew. Chem. 107:2179-2181 (1995)]. WO 99/00396 discloses
compositions of pentavalent and hexavalent ruthenium and osmium
carbene complex catalysts in admixture with dicyclopentadiene or
cycloolefins other than cyclohexene.
[0015] Therefore, the present invention relates to a compound of
the formula A-[X-(Y-Z).sub.p].sub.m[X'(Y'-Z').sub.q].sub.nB-Z''
(1), wherein [0016] one of m and n represents zero, one or a
numeral greater than one and the other one represents one or a
numeral greater than one, with the proviso that the sum of m and n
is at least two; [0017] p and q represent independently of one
another represent zero, one or a numeral greater than one; [0018] A
and B represent chain terminal groups from the chain transfer agent
A-B; [0019] X and X' independently of one another represent
unsaturated or hydrogenated repeating units from cycloolefins
polymerised by metathesis; [0020] Y and Y' represent identical or
different bivalent groups; and [0021] Z, Z' and Z'' independently
of one another represent alkoxy ether groups selected from the
group consisting of hydroxy-C.sub.2-C.sub.5alkoxy,
dihydroxy-C.sub.3-C.sub.7alkoxy,
hydroxy-C.sub.2-C.sub.3alkoxy-poly-C.sub.2-C.sub.3alkoxy,
dihydroxy-C.sub.2-C.sub.3alkoxy-poly-C.sub.2-C.sub.3alkoxy and
C.sub.1-C.sub.4alkoxy-poly-C.sub.2-C.sub.3alkoxy; or [0022] Z, Z'
and Z'' independently of one another represent alkoxy ether groups
selected from the group consisting of
dihydroxy-C.sub.3-C.sub.7alkoxy and
dihydroxy-C.sub.2-C.sub.3alkoxy-poly-C.sub.2-C.sub.3alkoxy, wherein
hydroxy is etherified by another group A-X''-B, [0023] wherein A-B
represent chain terminal groups from the chain transfer agent A-B
and X'' represents unsaturated or hydrogenated repeating units from
cycloolefins polymerised by metathesis.
[0024] The terms and definitions used in the description of the
present invention preferably have the following meanings:
[0025] In the compound (I) one of m and n represents zero, one or a
numeral greater than one and the other one represents one or a
numeral greater than one. The sum of m and n is at least two. The
indices m and n have no real upper limits. In a preferred
embodiment, the sum of m and n has a range from 2 to 50, preferably
5 to 20, whereas 5 to 10 are particularly preferred. In another
preferred embodiment, one of m and n is a numeral from 2 to 50 and
the other one is zero.
[0026] The indices p and q independently of one another represent
zero, one or a numeral greater than one and the other one
represents one or a numeral greater than one. In a preferred
embodiment, p and q are zero. In that event, there are no groups Z
and Z' attached to either one of X and X'. Only Z'' has the
meanings mentioned above.
[0027] The formula I comprises any polymeric compound wherein the
lowest total number of repeating units X and X' is two. In that
event, the sum of m and n is two. The formula I comprises any
polymeric compounds of low molecular weight, such as oligomers or
cooligomers, or homopolymers and copolymers of higher molecular
weight, for example block, multi-block or gradient copolymers as
well as copolymers characterised by a random, hyper-branched,
star-shaped or dendritic arrangement of the polymer units as well
as graft copolymers.
[0028] The compounds (I) are obtainable by metathesis
polymerisation, as opposed to other methods of polymerisation, such
as ionic or free radical polymerisation. Metathesis polymerisation
is characterised by the ring-opening polymerisation of cycloalkenes
initiated by olefin metathesis catalysts, cf. Concise Encyclopaedia
of Polymer Science and Engineering, J. I. Kroschwitz (editor), J.
Wiley & Sons USA, 1990 Edition, ISBN 0-471-51253-2, pg. 611.
Representative cycloalkenes polymerisable by this method include
dicyclopentadiene, norbornadiene, norbornene, cyclooctene and
cyclooctadiene.
[0029] The polymerisation by metathesis is performed in the
presence of chain transfer agents (CTA) of the formula A-B wherein
A and B represent chain terminal groups. Chain transfer agents are
used to regulate and limit the molecular weight in a polymer
reaction, cf. F. W. Billmeyer, Polymer Science, ISBN 0-471-03196-8,
pg. 63.
[0030] Suitable chain transfer agents are open chain alkenes, e.g.
propylene, n-butene, n-hexene or n-octene, which are present in the
compound (I) as identical or different terminal alkyl groups A and
B. In a particularly preferred embodiment A and B are different and
p and q are zero. One of A and B represent methyl and the other one
represent linear C.sub.2-C.sub.7alkyl, e.g. n-propyl, n-pentyl or
n-heptyl.
[0031] In that preferred embodiment the alkoxy ether group Z'',
particularly dihydroxy-C.sub.3-C.sub.5alkoxy, methoxy-polyethoxy,
polyethoxy, methoxy-poly-n-propoxy, and ethoxy-poly-n-propoxy, is
attached to the terminal groups of longer chain length. In the
event that propylene is substituted by the alkoxy ether groups,
e.g. allyl polyalkoxy ethers, one of A and B is methyl and the
other one is ethyl substituted by polyalkoxy. There are no alkoxy
ether groups substituting the repeating units X and X'.
[0032] The term cycloolefin polymerised or polymerisable by
metathesis defining X and X'' includes monocyclic cycloolefins
other than cyclohexene and polycyclic, polycyclic condensed (fused)
or bridged or polycyclic condensed (fused) and bridged
cycloolefins. The individual rings in these cycloolefins consist of
3 to 16, especially 3 to 12, and preferably 3 to 8 ring members and
may contain heteroatoms selected from the group consisting of O, S,
N and Si and additional substituents selected from the group
consisting of C.sub.1-C.sub.4alkyl, e. g. methyl or ethyl,
C.sub.1-C.sub.4alkoxy, e. g. methoxy or ethoxy, halogen, e.g.
chloro or bromo, cyano and trifluoromethyl.
[0033] A preferred group includes cycloolefins polymerised by
metathesis selected from the group consisting of cyclopropene,
cyclobutene, cyclopentene, cycloheptene, cyclooctene,
cyclopentadiene, dicyclopentadiene, cyclohexadiene,
cycloheptadiene, cyclooctadiene, norbornadiene, norbornene and
norbornene derivatives.
[0034] Another preferred group of cycloolefins includes bi-, tri-,
tetra- and pentacyclic bridged cycloolefins obtainable by a
Diels-Alder type addition reaction of dienes with so-called
dienophiles. The individual rings in these bridged cycloolefinic
adducts may be condensed with monocyclic or bicyclic carbocyclic
aromatic groups, such as benzene or naphthalene, or with monocyclic
or bicyclic heterocyclic aromatic groups, such as thiophene, furan,
pyridine or quinoline.
[0035] This preferred group of cycloolefins includes carbocyclic
bi-, tri-, tetra- and pentacyclic bridged cycloolefins obtainable
by a Diels-Alder type addition reaction, especially cycloolefins by
Diels-Alder reaction of cyclopentadiene with suitable
dienophiles.
[0036] A preferred group of cycloolefins of this type includes
monomers based on norbornene and norbornadiene selected from the
group consisting of norbornene-2, 5-methoxycarbonylnorbornene-2,
5-methyl-5-methoxycarbonyl-norbornene-2, 5-cyanonorbornene-2,
5-methyl-5-cyanonorbornene, 5,5-dicyano-norbornene-2,
1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthaline,
6-methyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthaline,
6-methyl-6-methoxycarbonyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydron-
aphthaline,
6-methoxycarbonyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalin-
e,
6-cyano-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthaline,
6-ethyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthaline,
6-ethylidene-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthaline,
6,7-dimethyl-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthaline,
1,4-dimethano-1,4,4a,9a-tetrahydrofluorene, dicyclopentadiene,
tricyclopentadiene, tetracyclopentadiene, tetracyclododecene and
methyl tetracyclododecene.
[0037] The bivalent groups Y and Y' are present in the event that
one of p and q is one or a numeral greater than one. Preferred
meanings of Y and Y' are --C(.dbd.O)--, --O--C(.dbd.O)-- and
C.sub.1-C.sub.8alkylene, e.g. ethylene.
[0038] In the compound (I) Z, Z' and Z'' independently of one
another represent alkoxy ether groups selected from the group
consisting of hydroxy-C.sub.2-C.sub.5alkoxy,
dihydroxy-C.sub.3-C.sub.7alkoxy,
hydroxy-C.sub.2-C.sub.3alkoxy-poly-C.sub.2-C.sub.3alkoxy and
C.sub.1-C.sub.4alkoxy-poly-C.sub.2-C.sub.3alkoxy. In a preferred
embodiment of the invention p and q are zero. In that event there
are no groups Z and Z' attached to either one of X and X'. Only Z''
has the meanings mentioned above.
[0039] Hydroxy-C.sub.2-C.sub.5alkoxy is, for example
2-hydroxyethoxy or 2- or 3-n-hydroxypropoxy.
[0040] Dihydroxy-C.sub.3-C.sub.7alkoxy is, for example,
2,3-dihydroxypropoxy or 2,3- or 3,4-dihydroxy-n-butoxy.
[0041] Hydroxy-C.sub.2-C.sub.3alkoxy-poly-C.sub.2-C.sub.3alkoxy is
a substituent derived from polyethylene glycol or polypropylene
glycol (=polyethylene oxide or polypropylene oxide) or mixed
polymerisates thereof and is represented by the following partial
formula HO--(CH.sub.2).sub.2-3--O--[(CH.sub.2).sub.2-3--O].sub.a--
(A), wherein a is a numeral from 1 to about 1.0.times.10.sup.5,
preferably 1 to 2000, especially 1 to 200.
[0042] Dihydroxy-C.sub.2-C.sub.3alkoxy-poly-C.sub.2-C.sub.3alkoxy
is a substituent derived from polyethylene glycol or polypropylene
glycol (=polyethylene oxide or polypropylene oxide) or mixed
polymerisates thereof and is represented by the following partial
formula HO--[(CH.sub.2).sub.2-3--O].sub.a--(CH.sub.2).sub.2-3--OH
(A'), wherein a is a numeral from 1 to about 1.0.times.10.sup.5,
preferably 1 to 2000, especially 1 to 200.
[0043] Hydroxy-C.sub.2-C.sub.3alkoxy-poly-C.sub.2-C.sub.3alkoxy is
derived from polyethylene glycol and is represented by the
following partial formula
HO--C.sub.2H.sub.4--O--(C.sub.2H.sub.4--O).sub.a-- (A''), wherein
a' is a numeral from 1 to about 1.0.times.10.sup.5, preferably 1 to
2000, especially 1 to 200.
[0044] Hydroxy-C.sub.2-C.sub.3alkoxy-poly-C.sub.2-C.sub.3alkoxy
derived from polypropylene glycol is represented by the following
partial formula HO--C.sub.3H.sub.6--O--(C.sub.3H.sub.6--O).sub.a--
(A'''), wherein a'' is a numeral from 1 to about
1.0.times.10.sup.5, preferably 1 to 2000, especially 1 to 200.
Hydroxy-C.sub.2-C.sub.3alkoxy-poly-C.sub.2-C.sub.3alkoxy preferably
has a linear structure.
[0045] C.sub.1-C.sub.4alkoxy-poly-C.sub.2-C.sub.3alkoxy is a
substituent derived from polyethylene glycol or polypropylene
glycol (=polyethylene oxide or polypropylene oxide) or mixed
polymerisates wherein the terminal hydroxy group is etherified with
C.sub.1-C.sub.4alkyl, preferably methyl or ethyl.
[0046] C.sub.1-C.sub.4alkoxy-poly-C.sub.2-C.sub.3alkoxy is
represented by the following partial formula
C.sub.1-C.sub.4alkoxy-(CH.sub.2).sub.2-3--O--[(CH.sub.2).sub.2-3--O].sub.-
a-- (B), wherein a is a numeral from 1 to about 1.0.times.10.sup.5,
preferably 1 to 2000, especially 1 to 200. Preferred meanings are
methoxy-polyethoxy, polyethoxy, methoxy-poly-n-propoxy and
ethoxy-poly-n-propoxy.
[0047] In another embodiment of the invention, Z, Z' and Z''
independently of one another represent alkoxy ether groups selected
from the group consisting of dihydroxy-C.sub.3-C.sub.7alkoxy and
dihydroxy-C.sub.2-C.sub.3alkoxy-poly-C.sub.2-C.sub.3alkoxy,
particularly
dihydroxy-C.sub.2-C.sub.3alkoxy-poly-C.sub.2-C.sub.3alkoxy (A'),
and wherein hydroxy is etherified by another group A-X''-B, wherein
A-B represent chain terminal groups from the chain transfer agent
A-B and X'' represents unsaturated or hydrogenated repeating units
from cycloolefins polymerised by metathesis. The synthesis of a
representative transfer agent is illustrated by the following
reaction sequence: ##STR1##
[0048] The "bivalent" chain transfer agent may then polymerise
another cycloolefin moiety as follows: ##STR2##
[0049] The present invention particularly relates to compounds (I),
wherein [0050] p and q represent zero; [0051] one of m and n
represents a numeral from 2 to 20 and the other one represents
zero; [0052] A and B represent chain terminal groups from the chain
transfer agent C.sub.3-C.sub.8alkene; [0053] X and X' independently
of one another represent an unsaturated or hydrogenated repeating
unit from cycloolefins polymerised by metathesis selected from the
group consisting of cyclopropene, cyclobutene, cyclopentene,
cycloheptene, cyclooctene, cyclopentadiene, dicyclopentadiene,
cyclohexadiene, cycloheptadiene, cyclooctadiene, norbornadiene,
norbornene and norbornene derivatives; [0054] Y and Y'
independently of one another represent bivalent groups selected
from the group consisting of --C(.dbd.O)--, --O--C(.dbd.O)-- and
C.sub.1-C.sub.8alkylene; and [0055] Z, Z' and Z'' independently of
one another represent an alkoxy ether group selected from the group
consisting of dihydroxy-C.sub.3-C.sub.5alkoxy, methoxy-polyethoxy,
polyethoxy, methoxy-poly-n-propoxy, and ethoxy-poly-n-propoxy.
[0056] Highly preferred are compounds (I), wherein p and q
represent zero; [0057] one of m and n represents a numeral from 2
to 20 and the other one represents zero; [0058] A and B represent
chain terminal groups from the chain transfer agent
C.sub.3-C.sub.8alkene; [0059] X and X' independently of one another
represent an unsaturated or hydrogenated repeating unit from
cycloolefins polymerised by metathesis selected from the group
consisting of cyclopentadiene, dicyclopentadiene, norbornadiene,
norbornene and norbornene derivatives; and [0060] Z'' represents an
alkoxy ether group selected from the group consisting of
dihydroxy-C.sub.3-C.sub.5alkoxy, methoxy-polyethoxy, polyethoxy,
methoxy-poly-n-propoxy, and ethoxy-poly-n-propoxy.
[0061] The following compounds are especially preferred: ##STR3##
wherein m represents a numeral from 5 to 20.
[0062] Another preferred group relates to compounds of the formulae
##STR4## wherein m represents a numeral from 5 to 20.
[0063] The present invention also relates to a polymerisable
composition comprising [0064] a) a catalytically effective amount
of a penta- or hexavalent ruthenium or osmium carbene catalyst
capable of performing ring opening metathesis polymerisation of
cycloolefins; and [0065] b) the chain transfer agent A-B and
monomers capable of forming a compound of the formula (I), wherein
A, B, X, X', Y, Y', Z, Z', Z'', p, q, m and n are as defined
above.
[0066] A suitable penta- or hexavalent ruthenium or osmium carbene
catalyst present in the composition mentioned above is described on
pages 12-44 of Olefin Metathesis and Metathesis Polymerization; K.
J. Ivin, J. C. Mol, Academic Press, ISBN 0-12-377045-9.
[0067] A particularly suitable penta- or hexavalent ruthenium or
osmium carbene catalyst is represented by the formulae ##STR5##
wherein [0068] Me represents ruthenium or osmium; [0069] L.sub.a
and L.sub.b independently of one another represent anionic ligands;
[0070] L.sup.1, L.sup.2 and L.sup.3 independently of one another
represent monodentate donor ligands; and [0071] R represents aryl,
arylthio, or C.sub.3-C.sub.5alkenyl.
[0072] The polymerisable compositions comprising as component a)
the penta- or hexavalent ruthenium or osmium carbene catalysts
(IIa) and (IIb) defined above and as component b) the chain
transfer agent capable of forming the compound (I) defined above
are a preferred embodiment of the invention.
[0073] The anionic ligands L.sub.a and L.sub.b are, for example,
hydride ions (H.sup.-) or are derived from inorganic or organic
acids, examples being halides, e.g. F.sup.-, Cl.sup.-, Br.sup.- or
I.sup.-, fluoro complexes of the type BF.sub.4.sup.-,
PF.sub.6.sup.-, SbF.sub.6.sup.- or AsF.sub.6.sup.-, anions of
oxygen acids, alcoholates or acetylides or anions of
cyclopentadiene.
[0074] The anions of oxygen acids can be, for example, the
sulphate, phosphate, perchlorate, perbromate, periodate,
antimonate, arsenate, nitrate, or carbonate ions, the anion of a
C.sub.1-C.sub.8carboxylic acid, such as formate, acetate,
propionate, butyrate, benzoate, phenylacetate, mono-, di- or
trichloro- or -fluoroacetate, sulphonates, for example methyl-,
ethyl-, propyl-, or n-butylsulphonate, trifluoromethylsulphonate
(triflate), phenylsulphonate or benzylsulphonate or
phenylsulphonate and benzylsulphonate substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy or halogen, especially
fluoro, chloro or bromo, for example tosylate, mesylate, brosylate,
p-methoxy- or p-ethoxyphenylsulphonate, pentafluorophenylsulphonate
or 2,4,6-triisopropylsulphonate.
[0075] Particularly preferred anionic ligands L.sub.a and L.sub.b
are H.sup.-, F.sup.-, Cl.sup.-, Br.sup.-, BF.sub.4.sup.-,
PF.sub.6.sup.-, SbF.sub.6.sup.-, AsF.sub.6.sup.-,
CF.sub.3SO.sub.3.sup.-, C.sub.6H.sub.5--SO.sub.3.sup.-,
4-methyl-C.sub.6H.sub.4--SO.sub.3.sup.-,
3,5-dimethyl-C.sub.6H.sub.3--SO.sub.3.sup.-,
2,4,6-trimethyl-C.sub.6H.sub.2--SO.sub.3.sup.- and
4-CF.sub.3--C.sub.6H.sub.4--SO.sub.3.sup.- and also
cyclopentadienyl (Cp.sup.-). Cl.sup.- is especially preferred.
[0076] In the compounds of the formulae IIa and IIb up to three
neutral ligands L.sup.1, L.sup.2 and L.sup.3 are
tertiary-substituted phosphine having 3-about 40, preferably 3-30,
and, with particular preference, 3-18 carbon atoms. The
tertiary-substituted phosphine is preferably a compound of the
formula ##STR6## in which R.sup.1, R.sup.2 and R.sup.3
independently of one another are C.sub.1-C.sub.20alkyl,
C.sub.3-C.sub.12cycloalkyl, C.sub.2-C.sub.11heterocycloalkyl,
C.sub.5-C.sub.12aryl, C.sub.1-C.sub.12heteroaryl or
C.sub.6-C.sub.14aralkyl, which may be substituted by one or more
substituents selected from the group consisting of
C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy,
C.sub.1-C.sub.6haloalkyl, C.sub.5-C.sub.12aryl, --NO.sub.2,
SO.sub.3.sup.-, ammonium and halogen; the radicals R.sup.1 and
R.sup.2 together are tetra- or pentamethylene, which may be
substituted by one or more substituents selected from the group
consisting of C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl,
NO.sub.2 and C.sub.1-C.sub.6alkoxy, or R.sup.1 and R.sup.2
represent tetra- or pentamethylene, which may be fused to 1 or 2
1,2-phenylene radicals, and wherein R.sup.3 is as defined
above.
[0077] Particular preferred are phosphines wherein R.sup.1, R.sup.2
and R.sup.3 are methyl, ethyl, n- or i-propyl, n-, i-, s- or
t-butyl, 1-, 2- or 3-pentyl, 1-, 2-, 3- or 4-hexyl, cyclopentyl,
cyclohexyl, phenyl, naphthyl or benzyl, e.g.
(i-C.sub.3H.sub.7).sub.3P, (C.sub.5H.sub.9).sub.3P and
(C.sub.6H.sub.11).sub.3P.
[0078] In the compounds of the formulae IIa and IIb one or two of
the neutral ligands L.sup.1, L.sup.2 and L.sup.3 are monodentate,
neutral e.sup.- donor ligands having electron donor properties, or
two ligands together are bidentate, neutral e donor ligands.
[0079] Such ligands are derived from heteroarenes, e.g.
heteroarenes selected from the group consisting of furan,
thiophene, pyrrole, pyridine, bis-pyridine, picolylimine,
.gamma.-pyran, .gamma.-thiopyran, phenanthroline, pyrimidine,
bis-pyrimidine, pyrazine, indole, coumarone, thionaphthene,
carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole,
benzimidazole, oxazole, thiazole, bis-thiazole, isoxazole,
isothiazole, quinoline, bis-quinoline, isoquinoline,
bis-isoquinoline, acridine, chromene, phenazine, phenoxazine,
phenothiazine, triazine, thianthrene, purine, bis-imidazole and
bis-oxazole.
[0080] These ligands may further be substituted by suitable
substituents selected from the group consisting of
C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy, carboxy,
C.sub.1-C.sub.6alkoxycarbonyl, C.sub.1-C.sub.6haloalkyl, nitro,
sulpho, ammonium and halogen.
[0081] Aryl and arylthio R is, for example phenyl or phenylthio or
phenyl and phenylthio substituted by one or more substituents
selected from the group consisting of C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkoxy, carboxy, C.sub.1-C.sub.6alkoxycarbonyl,
C.sub.1-C.sub.6haloalkyl, nitro, sulpho, ammonium and halogen.
[0082] C.sub.3-C.sub.5alkenyl R is, for example, vinyl, 1-, 2- or
3-propenyl, or the different butenyl, pentenyl or hexenyl isomers,
1,3-hexadienyl or 2,4,6-heptatrienyl or is ethylidene, 1- or
2-propylidene or 1-, 2- or 3-propylidene directly attached to the
carbene group. These substituents may be substituted with
additional substituents selected from the group consisting of
halogen, C.sub.1-C.sub.5alkoxy and phenyl, which in turn may be
substituted with C.sub.1-C.sub.5alkyl, halogen, or
C.sub.1-C.sub.5alkoxy.
[0083] The monomers and chain transfer agents can be present in an
amount of from 0.01 to 99% by weight, preferably from 0.1 to 95% by
weight, with particular preference from 1 to 90% by weight and,
with especial preference, from 5 to 80% by weight, based on the
monomers present in the composition.
[0084] The composition may comprise inert solvents. One particular
advantage is that in the case of liquid monomers metathesis
polymerisation can be carried out without the use of a solvent. A
further advantage is that the polymerisation can even be carried
out in water, polar and protic solvents or water/solvent
mixtures.
[0085] Examples of suitable inert solvents are protic polar and
aprotic solvents, which can be used alone or in mixtures of at
least two solvents. Examples are ethers (dibutyl ether,
tetrahydrofuran, dioxane, ethylene glycol monomethyl or dimethyl
ether, ethylene glycol monoethyl or diethyl ether, diethylene
glycol diethyl ether, triethylene glycol dimethyl ether),
halogenated hydrocarbons, etc.
[0086] In the context of the present invention, catalytic amounts
denote preferably an amount from 0.001 to 1.0 mol-%, with
particular preference from 0.01 to 0.5 mol-% and, with very
particular preference, from 0.01 to 0.1 mol-%, based on the amount
of monomer.
[0087] A particularly preferred embodiment of the invention relates
to a polymerisable composition comprising [0088] a) a catalytically
effective amount of a penta- or hexavalent ruthenium carbene
catalyst selected from the group consisting of ##STR7## [0089] b)
the chain transfer agent A-B and monomers capable of forming the
compound (I), wherein A, B, X, X', Y, Y', Z, Z', Z'', p, q, m and n
are as defined above.
[0090] Another embodiment of the invention relates to a composition
comprising [0091] .alpha.) a polymer obtainable from ethylenically
unsaturated polymerisable monomers or oligomers; [0092] .beta.) the
compound (I) wherein A, B, X, X', Y, Y', Z, Z', Z'', p, q, m and n
are as defined above.
[0093] Suitable polymers present as component .alpha.) in the
composition are obtained by conventional methods of polymerisation
from monomers or oligomers are selected from the group consisting
of monomeric or oligomeric alkenes, styrenes, conjugated dienes,
acrolein, vinyl acetate, vinyl pyrrolidone, vinyl imidazole, maleic
acid anhydride, acrylic acid, C.sub.1-C.sub.4alkyl acrylic acid or
amides, nitriles, anhydrides and salts of acrylic acid and
C.sub.1-C.sub.4alkyl acrylic acid, acrylic acid
C.sub.1-C.sub.24alkyl esters, C.sub.1-C.sub.4alkyl acrylic acid
C.sub.1-C.sub.24alkyl esters, vinyl halides and vinylidene
halides.
[0094] A preferred embodiment of the invention relates to
compositions wherein polyolefins are present as component
.alpha.).
[0095] Suitable polyolefins are polymers of monoolefins and
diolefins, for example polypropylene, polyisobutylene,
polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or
polybutadiene, as well as polymers of cycloolefins, for instance of
cyclopentene or norbornene, polyethylene (which optionally can be
crosslinked), for example high density polyethylene (HDPE), high
density and high molecular weight polyethylene (HDPE-HMW), high
density and ultrahigh molecular weight polyethylene (HDPE-UHMW),
medium density polyethylene (MDPE), low density polyethylene
(LDPE), linear low density polyethylene (LLDPE), (VLDPE) and
(ULDPE).
[0096] These polyolefins are obtainable by known methods, such as
radical polymerisation (normally under high pressure and at
elevated temperature) or catalytic polymerisation using a catalyst
that normally contains one or more than one metal of groups IVb,
Vb, VIb or VIII of the Periodic Table. These metals usually have
one or more than one ligand, typically oxides, or halide,
alcoholate, ester, ether, amine, alkyl, alkenyl and/or aryl groups
that may be either p- or s-coordinated. These metal complexes may
be in the free form or fixed on substrates, typically on activated
magnesium chloride, titanium(III) chloride, alumina or silicon
oxide. These catalysts may be soluble or insoluble in the
polymerisation medium. The catalysts can be used in the optional
presence of further activators, such as metal alkyl, metal hydride,
metal alkyl halide, metal alkyl oxide or metal alkyloxane groups,
said metals being elements of groups Ia, IIa and/or IIIa of the
Periodic Table. The activators may be modified conveniently with
further ester, ether, and amine or silyl ether groups. These
catalyst systems are usually termed Phillips, Standard Oil Indiana,
Ziegler (-Natta), TNZ (DuPont), metallocene or single site
catalysts (SSC).
[0097] Other polyolefins present in the composition defined above
are [0098] Mixtures of the polymers mentioned above, for example
mixtures of polypropylene with polyisobutylene, polypropylene with
polyethylene, for example PP/HDPE, PP/LDPE, and mixtures of
different types of polyethylene, for example LDPE/HDPE; [0099]
Copolymers of monoolefins and diolefins with each other or with
other vinyl monomers, for example ethylene/propylene copolymers,
linear low density polyethylene (LLDPE) and mixtures thereof with
low density polyethylene (LDPE), propylene/but-1-ene copolymers,
propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,
ethylene/hexene copolymers, ethylene/methylpentene copolymers,
ethylene/heptene copolymers, ethylene/octene copolymers,
propylene/butadiene copolymers, isobutylene/isoprene copolymers,
ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate
copolymers, ethylene/vinyl acetate copolymers and their copolymers
with carbon monoxide or ethylene/acrylic acid copolymers and their
salts (ionomers) as well as terpolymers of ethylene with propylene
and a diene, such as hexadiene, dicyclopentadiene or
ethylidene-norbornene; and mixtures of such copolymers with one
another and with polymers mentioned above, for example
polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl
acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers
(EAA), LLDPE/EVA, LLDPE/EAA and alternating or random
polyalkylene/carbon monoxide copolymers and mixtures thereof with
other polymers, for example polyamides.
[0100] Particularly preferred are polyethylene, polyethylene
blends, polypropylene, propylene copolymers and polypropylene
blends.
[0101] Polyethylene present in the composition is preferred having
a melt index or melt flow value, in the range of about 0.01 to
about 20 g/10 min., as measured by ASTM-D-1238, condition E, and a
density in the range of about 0.9 to about 0.96 g/cm.sup.3. This
includes the branched polymers made at high pressure with a
free-radical initiator and those made at low, medium, or high
pressure using a coordination catalyst, which gives linear (i.e.
substantially non-branched) polymers. Those made using a
free-radical initiator (e.g. peroxo compounds) have become known in
the art as "low density polyethylene" (LDPE) and those made using a
coordination catalyst (e.g. a "Ziegler-type catalyst) have become
known as "high density polyethylene" (HDPE).
[0102] Also preferred are commercially available "linear low
density polyethylenes" (LLDPE) which are prepared using a
coordination catalyst, but which, because of the presence of minor
amounts of copolymerised higher olefins (especially olefins of 4-10
carbon atoms), have a density lower than HDPE, yet the arrangement
of polymerised molecular units is of the linear type.
[0103] Particularly preferred are polyethylene types of the LLDPE
variety, especially those which have a melt flow value in the range
of about 0.1-10 and sufficient comonomer units to give a density in
the range of about 0.9 to about 0.935 g/cm.sup.3, such comonomer
units being an aliphatic hydrocarbon olefin of from 4 to 8 carbon
atoms, including isomers in that range. These LLDPE polymers are
recognized in the art as having excellent strength, resistance to
tear propagation as shown by Dart Impact and Elmendorf Tear, and
exhibit good resistance to tearing or puncturing when stressed
against articles having protuberances. This preference for the
LLDPE variety is especially important in food packaging
applications and most especially in packaging of red meat.
[0104] The composition of the invention can comprise additives
suitable for polymers, which additives are preferably used as
formulating auxiliaries to improve together with the compounds of
the formula (I) the chemical and physical properties of the
polymers containing these additives. The auxiliaries can be present
in high proportions, for example, in amounts of up to 70% by
weight, preferably from 1 to 70% by weight, more preferably from 5
to 60% by weight, with particular preference from 10 to 50% by
weight and with especial preference from 10 to 40% by weight, based
on the composition. Such auxiliaries have been disclosed in large
numbers and are set out by way of example in the following list of
auxiliaries: antioxidants selected from the group consisting of
alkylated monophenols, alkylthiomethylphenols, hydroquinones and
alkylated hydroquinones, tocopherols, hydroxylated thiodiphenyl
ethers, alkylidene-bis-phenols, O-, N- and S-benzyl compounds,
hydroxybenzylated malonates, aromatic hydroxybenzyl compounds,
triazine compounds, benzylphosphonates, acylaminophenols, esters
and amides of .beta.-(3,5-di-t-butyl-4-hydroxyphenyl)propionic
acid, .beta.-(3,5-di-t-butyl-4-hydroxy-3-methylphenyl)propionic
acid, or .beta.-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid,
ascorbic acid, aminic antioxidants, light stabilisers, phosphites,
phosphines, phosponites, hydroxylamines, nitrones, thiosynergists,
peroxide scavengers, polyamide stabilisers, basic co-stabilisers,
nucleating agents, fillers and reinforcing agents, plasticisers,
lubricants, emulsifiers, pigments, Theological additives, levelling
assistants, optical brighteners, flame proofing agents, antistatic
agents, blowing agents, benzofuranones and indolinones.
[0105] Such auxiliaries have been disclosed in large numbers and
are set out by way of example in the following list of
auxiliaries:
[0106] 1. Antioxidants [0107] 1.1. Alkylated monophenols, for
example 2,6-di-t-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol,
2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol,
2,6-di-t-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-t-butyl-4-methoxymethylphenol, linear or side chain-branched
nonylphenols; such as 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.
[0108] 1.2. Alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-t-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-didodecylthiomethyl-4-nonylphenol. [0109] 1.3. Hydroquinones
and alkylated hydroquinones, for example
2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone,
2,5-di-t-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,
2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole,
3,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl
stearate, bis(3,5-di-t-butyl-4-hydroxyphenyl)adipate. [0110] 1.4.
Tocopherols, for example .alpha.-, .beta.-, .gamma.- or
.delta.-tocopherols and mixtures thereof (vitamin E). [0111] 1.5.
Hydroxylated thiodiphenyl ethers, for example
2,2'-thiobis(6-t-butyl-4-methylphenol),
2,2'-thiobis(4-octylphenol),
4,4'-thiobis(6-t-butyl-3-methylphenol),
4,4'-thiobis(6-t-butyl-2-methylphenol),
4,4'-thiobis(3,6-di-sec-amylphenol),
4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)disulphide. [0112] 1.6.
Alkylidene-bis-phenols, for example
2,2'-methylene-bis(6-t-butyl-4-methylphenol),
2,2'-methylene-bis(6-t-butyl-4-ethylphenol),
2,2'-methylene-bis[4-methyl-6-(.alpha.-methylcyclohexyl)phenol],
2,2'-methylene-bis(4-methyl-6-cyclohexylphenol),
2,2'-methylene-bis(6-nonyl-4-methylphenol),
2,2'-methylene-bis(4,6-di-t-butylphenol),
2,2'-ethylidene-bis(4,6-di-t-butylphenol),
2,2'-ethylidene-bis(6-t-butyl-4-isobutylphenol),
2,2'-methylene-bis[6-(.alpha.-methylbenzyl)-4-nonylphenol],
2,2'-methylene-bis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol],
4,4'-methylene-bis(2,6-di-t-butylphenol),
4,4'-methylene-bis(6-t-butyl-2-methylphenol),
1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)butane,
2,6-bis(3-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,
1,1,3-tris(5-t-butyl-4-hydroxy-2-methylphenyl)butane,
1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,
ethylene glycol bis[3,3-bis(3'-t-butyl-4'-hydroxyphenyl)butyrate],
bis(3-t-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene,
bis[2-(3'-t-butyl-2'-hydroxy-5'-methylbenzyl)-6-t-butyl-4-methylphenyl]te-
rephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane,
2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane,
2,2-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,
1,1,5,5-tetra-(5-t-butyl-4-hydroxy-2-methylphenyl)pentane. [0113]
1.7. O-, N- and S-benzyl compounds, for example
3,5,3',5'-tetra-t-butyl-4,4'-dihydroxydibenzyl ether, octadecyl
4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl
4-hydroxy-3,5-di-t-butylbenzylmercaptoacetate,
tris(3,5-di-t-butyl-4-hydroxybenzyl)-amine,
bis(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,
bis(3,5-di-t-butyl-4-hydroxybenzyl)sulphide, isooctyl
3,5-di-t-butyl-4-hydroxybenzylmercaptoacetate. [0114] 1.8.
Hydroxybenzylated malonates, for example dioctadecyl
2,2-bis(3,5-di-t-butyl-2-hydroxybenzyl)malonate, dioctadecyl
2-(3-t-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecyl
mercaptoethyl-2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate,
di-[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-t-butyl-4-hydroxyb-
enzyl)malonate. [0115] 1.9. Aromatic hydroxybenzyl compounds, for
example
1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene-
,
1,4-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,
2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)phenol. [0116] 1.10.
Triazine compounds, for example
2,4-bisoctylmercapto-6-(3,5-di-t-butyl-4-hydroxyanilino)-1,3,5-triazine,
2-octylmercapto-4,6-bis(3,5-di-t-butyl-4-hydroxyanilino)-1,3,5-triazine,
2-octylmercapto-4,6-bis(3,5-di-t-butyl-4-hydroxyphenoxy)-1,3,5-triazine,
2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,
1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazi-
ne, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
[0117] 1.11. Benzylphosphonates, for example dimethyl
2,5-di-t-butyl-4-hydroxybenzyl-phosphonate, diethyl
3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl
3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl
5-t-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of
the monoethyl ester of 3,5-di-t-butyl-4-hydroxybenzylphosphonic
acid. [0118] 1.12. Acylaminophenols, for example
4-hydroxylauranilide, 4-hydroxystearanilide, octyl
N-(3,5-di-t-butyl-4-hydroxyphenyl)carbamate. [0119] 1.13. Esters of
.beta.-(3,5-di-t-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(2-hydroxyethyl)isocyanurate,
N,N'-bis(2-hydroxyethyl)oxalamide, 3-thiaundecanol,
3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. [0120]
1.14. Esters of
.beta.-(5-t-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(2-hydroxyethyl)isocyanurate,
N,N'-bis(2-hydroxyethyl)oxalamide, 3-thiaundecanol,
3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. [0121]
1.15. 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(2-hydroxyethyl)isocyanurate,
N,N'-bis(2-hydroxyethyl)-oxalamide, 3-thiaundecanol,
3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. [0122]
1.16. Esters of 3,5-di-t-butyl-4-hydroxyphenylacetic 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(2-hydroxyethyl)isocyanurate,
N,N'-bis(2-hydroxyethyl)-oxalamide, 3-thiaundecanol,
3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. [0123]
1.17. Amides of .beta.-(3,5-di-t-butyl-4-hydroxyphenyl)propionic
acid, e.g.
N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropionyl)hexamethylenediamid-
e,
N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,
N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropionyl)hydrazide,
N,N'-bis[2-(3-[3,5-di-t-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide
(Naugard.RTM. XL-1 from Uniroyal). [0124] 1.18. Ascorbic acid
(vitamin C). [0125] 1.19. Aminic antioxidants, for example
N,N'-diisopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylenediamine,
N,N'-bis(1,4-dimethyl-pentyl)-p-phenylenediamine,
N,N'-bis(1-ethyl-3-methyl-pentyl)-p-phenylenediamine,
N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine,
N,N'-diphenyl-p-phenylenediamine,
N,N'-di-(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-toluenesulphonamido)-diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyldiphenylamine, 4-isopropoxydiphenylamine,
N-phenyl-1-naphthylamine, N-(4-t-octylphenyl)-1-naphthylamine,
N-phenyl-2-naphthylamine, octylated diphenylamine, for example
p,p'-di-t-octyldiphenylamine, 4-n-butylaminophenol,
4-butyrylaminophenol, 4-nonanoylaminophenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
di-(4-methoxyphenyl)amine,
2,6-di-t-butyl-4-dimethylaminomethylphenol,
2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetramethyl-4,4'-diamino-diphenylmethane,
1,2-di[(2-methylphenyl)amino]ethane, 1,2-diphenylaminopropane,
(o-tolyl)biguanide, di-[4-(1',3'-dimethylbutyl)phenyl]amine,
t-octylated N-phenyl-1-naphthylamine, a mixture of mono- and
dialkylated t-butyl/t-octyldiphenylamines, a mixture of mono- and
dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated
dodecyldiphenylamines, a mixture of mono- and dialkylated
isopropyl/isohexyl-diphenylamines, mixtures of mono- and
dialkylated t-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a
mixture of mono- and dialkylated t-butyl/t-octyl-phenothiazines, a
mixture of mono- and dialkylated t-octyl-phenothiazines,
N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,
N,N-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine,
bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,
2,2,6,6-tetramethylpiperidin-4-one and
2,2,6,6-tetramethylpiperidin-4-ol.
[0126] 2. Other UV-Absorbers and Light Stabilisers [0127] 2.1.
Acrylates, for example ethyl .alpha.-cyano-.beta.,.beta.-diphenyl
acrylate or isooctyl .alpha.-cyano-.beta.,.beta.-diphenyl acrylate,
methyl .alpha.-carbomethoxycinnamate, methyl
.alpha.-cyano-.beta.-methyl-p-methoxycinnamate or butyl
.alpha.-cyano-.beta.-methyl-p-methoxycinnamate, methyl
.alpha.-carbomethoxy-p-methoxycinnamate and
N-(.beta.-carbomethoxy-.beta.-cyanovinyl)-2-methylindoline. [0128]
2.2. Nickel compounds, for example nickel complexes of
2,2'-thio-bis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1-
or 1:2-complex, with or without additional ligands, such as
n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel
dibutyldithiocarbamate, nickel salts of monoalkyl esters, such as
of the methyl or ethyl ester, of
4-hydroxy-3,5-di-t-butylbenzylphosphonic acid, nickel complexes of
ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecyl ketoxime,
nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or
without additional ligands. [0129] 2.3. Sterically hindered amines,
for example bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,
bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate,
bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,
bis(1,2,2,6,6-pentamethylpiperidyl)
n-butyl-3,5-di-t-butyl-4-hydroxybenzylmalonate, the condensate of
1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic
acid, the linear or cyclic condensates of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-t-octylamino-2,6-dichloro-1,3,5-s-triazine,
tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetraoate,
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-t-butyl-
benzyl)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, the 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-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazi-
ne 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, the condensate of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, the condensate 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-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-oxospiro[4.5]decane,
the reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
and epichlorohydrine,
1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)-
ether,
N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethy-
lenediamine, the 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,
the reaction product of maleic anhydride-.alpha.-olefin copolymer
and 2,2,6,6-tetramethyl-4-aminopiperidine or
1,2,2,6,6-pentamethyl-4-aminopiperidine. [0130] 2.4. Oxalamides,
for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxy-oxanilide,
2,2'-dioctyl-oxy-5,5'-di-t-butyloxanilide,
2,2'-didodecyloxy-5,5'-di-t-butyloxanilide,
2-ethoxy-2'-ethyloxanilide,
N,N'-bis(3-dimethylaminopropyl)oxalamide,
2-ethoxy-5-t-butyl-2'-ethyloxanilide and its mixture with
2-ethoxy-2'-ethyl-5,4'-di-t-butyloxanilide and mixtures of o- and
p-methoxy- and of o- and p-ethoxy-disubstituted oxanilides. [0131]
2.5. 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)-4,6bis(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-butyloxypropyloxy)phenyl]-4,6-bis(2,4--
dimethylphenyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)-phenyl]-4,6-bis(2,4-dimeth-
ylphenyl)-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-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimeth-
ylphenyl)-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-hydroxy-propoxy)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.
[0132] 3. Metal deactivators, for example, N,N'-diphenyloxalamide,
N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine,
N,N'-bis(3,5-di-t-butyl-4-hydroxyphenyl-propionyl)hydrazine,
3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl
dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl
bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide,
N,N'-bis(salicyloyl)oxalyl dihydrazide,
N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
[0133] 4. Phosphites, phosphines and phosphonites, for example
triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl
phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite,
trioctadecyl phosphite, trimethylphosphine, tri-n-butylphosphine,
triphenylphosphine, distearyl pentaerythritol diphosphite,
tris(2,4-di-t-butylphenyl)phosphite, diisodecyl pentaerythritol
diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite,
bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite,
bisisodecyloxypentaerythritol diphosphite,
bis(2,4-di-t-butyl-6-methylphenyl)pentaerythritol diphosphite,
bis(2,4,6-tri-t-butylphenyl)pentaerythritol diphosphite, tristearyl
sorbitol triphosphite, tetrakis(2,4-di-t-butylphenyl)
4,4'-biphenylene diphosphonite,
6-isooctyloxy-2,4,8,10-tetra-t-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphoc-
in,
6-fluoro-2,4,8,10-tetra-t-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphos-
phocin, bis(2,4-di-t-butyl-6-methylphenyl)methyl phosphite,
bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite,
2,2',2''-nitrilo[triethyl-tris(3,3',5,5''tetra-t-butyl-1,1'-biphenyl-2,2'-
-diyl)phosphite],
2-ethylhexyl(3,3',5,5'-tetra-t-butyl-1,1'-biphenyl-2,2'-diyl)phosphite.
[0134] Particular preference is given to using the following
phosphites: [0135] tris(2,4-Di-t-butylphenyl)phosphite
(Irgafos.RTM.168, Ciba Specialty Chemicals), [0136]
tris(nonylphenyl)phosphite and the phosphites selected from the
group comprising the structural formulae (a), (b), (c), (d), (e),
(f) and (g) given below: ##STR8##
[0137] 5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,
N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,
N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,
N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,
N-hexadecyl-N-octadecylhydroxylamine,
N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine
from hydrogenated tallow fatty amines.
[0138] 6. Nitrones, for example N-benzyl .alpha.-phenyl nitrone,
N-ethyl .alpha.-methyl nitrone, N-octyl .alpha.-heptyl nitrone,
N-lauryl .alpha.-undecyl nitrone, N-tetradecyl .alpha.-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,
and nitrones derived from N,N-dialkylhydroxylamines prepared from
hydrogenated tallow fatty amines.
[0139] 7. Thiosynergists, for example dilauryl thiodiproprionate or
distearyl thiodipropionate.
[0140] 8. Peroxide scavengers, for example esters of
.beta.-thiodipropionic acid, for example the lauryl, stearyl,
myristyl or tridecyl esters, mercaptobenzimidazole, the zinc salt
of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate,
dioctadecyl disulphide, pentaerythritol
tetrakis(.beta.-dodecylmercapto)propionate.
[0141] 9. Polyamide stabilisers, for example copper salts in
combination with iodides and/or phosphorus compounds and salts of
divalent manganese.
[0142] 10. Basic co-stabilisers, for example melamine,
polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea
derivatives, hydrazine derivatives, amines, polyamides,
polyurethanes, alkali metal salts and alkaline earth metal salts of
higher fatty acids, for example calcium stearate, zinc stearate,
magnesium behenate, magnesium stearate, sodium ricinoleate,
potassium palmitate, antimony pyrocatecholate or zinc
pyrocatecholate.
[0143] 11. Nucleating agents, for example inorganic substances,
such as talc, metal oxides, such as titanium dioxide or magnesium
oxide, phosphates, carbonates or sulphates of, preferably, alkaline
earth metals; organic compounds, such as mono- or polycarboxylic
acids and their salts, such as 4-t-butylbenzoic acid, adipic acid,
diphenyl acetic acid, sodium succinate or sodium benzoate; and
polymeric compounds, for example ionic copolymers (ionomers).
[0144] 12. Fillers and reinforcing agents, for example calcium
carbonate, silicates, glass fibres, glass beads, talc, kaolin,
mica, barium sulphate, metal oxides and hydroxides, carbon black,
graphite, wood flour and flours or fibres of other natural
products, and synthetic fibres.
[0145] 13. Benzofuranones and indolinones, as described, for
example, in U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S.
Pat. No. 5,175,312, U.S. Pat. No. 5,216,052; U.S. Pat. No.
5,252,643; DE-A-4 316 611; DE-A-4 316 622; DE-A-4 316 876; EP-A-0
589 839 or EP-A-0 591 102, or
3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-t-butylbenzofuran-2-one,
5,7-di-t-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,
3,3'-bis[5,7-di-t-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],
5,7-di-t-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,
3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-t-butylbenzofuran-2-one,
3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-t-butylbenzofuran-2-one,
3-(3,4-dimethylphenyl)-5,7-di-t-butylbenzofuran-2-one,
3-(2,3-dimethylphenyl)-5,7-di-t-butylbenzofuran-2-one.
[0146] 14. Other additives, for example plasticisers, lubricants,
emulsifiers, pigments, Theological additives, catalysts, levelling
assistants, optical brighteners, flame proofing agents, antistatic
agents or blowing agents.
[0147] The mixing of the components of the composition, the polymer
obtainable from ethylenically unsaturated polymerisable monomers or
oligomers, component .alpha.), with the compound (I), component
.beta.), is carried out by known methods, e.g. by commonly used
techniques, such as roll-milling, mixing in a Banbury type mixer,
or mixing in an extruder barrel and the like.
[0148] Conveniently, the compound (I) acting as the antifog agent
can also be added substantially simultaneously or sequentially with
any other additives (colorants, tackifiers, slip agents, block
agents, and the like), which may be desired in certain instances.
The compound (I) may also be preblended with other additives
followed by adding the blend to the polymer. For easier
batch-to-batch control of quality, it may be preferred to employ
concentrated master batches of polymer/agent blends, which are
subsequently blended, as portions, to additional quantities of
polymer to achieve the final desired formulation.
[0149] It is well known in the art that polybutene or
polyisobutylene is an effective tackifier or cling agent when mixed
in polyethylene. The polybutenes or polyisobutylenes usually
employed for this purpose are generally used in small quantities.
The use of such tackifiers is preferred in certain of the
formulations contemplated as being within the purview of the
present invention, especially in meat packaging (and the like)
where it is desired that substantially no liquid leaks occur during
the packaging operation until heat-sealed, or during shipping,
storage, and handling after being heat-sealed.
[0150] The process for the production of films of polyolefins is
well-known and includes the techniques of casting films as thin
sheets through narrow slit dies, and the blown-film technique
wherein an extruded tube of molten polymer is inflated to the
desired "bubble" diameter and/or film thickness before being cooled
and collected or further processed. These present formulations are
also suitable in coextrusion fabrication of films wherein two or
more films comprise a multi-layer structure. The compound (I) can
exude through an adjacent film layer, which does not contain the
compound (I), thereby rendering the adjacent layer resistant to
fogging.
[0151] The polymer films of this invention with antifog properties
are advantageously used for greenhouse films. Therefore, the
invention also comprises the method for increasing the antifog
properties of polymers, which comprises incorporating within the
film polymer material a compound (I).
[0152] The polymer films of this invention are also advantageously
used for films used for food packaging applications. Therefore the
invention also comprises the method for incorporating within film
material for food packaging the compound (I).
[0153] The following examples illustrate the invention without
limiting its scope.
EXAMPLE 1
[0154] Oligomers with Monovalent Chain Transfer Agents:
##STR9##
[0155] 150 ml toluene are given to a 500 ml round bottomed flask,
equipped with a thermometer, mechanical stirrer, condenser,
dropping funnel and nitrogen inlet and a nitrogen atmosphere is
provided. The catalyst
bis(tricyclopentylphosphine)dichloro(3-methyl-2-butenylidene)rut-
henium (APT Cat ASMC 716) and chain transfer agent are added at
room temperature under nitrogen. 50 g (0.53 mol) 2-norbornene,
dissolved in 350 ml toluene, are dropped during 1 hour into the
flask at 38-45.degree. C. To complete the reaction, the reaction
mixture is kept at 40.degree. C. for 6 hours (cf. Table 1,
compounds 1.1-1.4).
[0156] The reaction mixture is poured without purification to an
autoclave. After rinsing with nitrogen the reaction mixture is
hydrogenated at 100.degree. C. and 30 bar for 8 hours. After
cooling to room temperature the reaction mixture is filtered
through a Celite.RTM. panel on a Buchner filter and concentrated in
the vacuum, which yields the desired product (cf. Table 2,
Compounds 2.1-2.4). TABLE-US-00001 TABLE 1 Com- Cat./ Monomer/
pound Monomer Chain transfer agent CTA No. [mol/mol] (CTA)
[mol/mol] M.sub.n M.sub.w M.sub.w/M.sub.n 1.1 1/1000 ##STR10##
1/0.20 1433 1940 1.35 1.2 1/1000 ##STR11## 1/0.125 2034 2070 1.33
1.3 1/1000 ##STR12## 1/0.10 2051 3540 1.73 1.4 1/1000 ##STR13##
1/0.20 1043 1418 1.36
[0157] TABLE-US-00002 TABLE 2 Com- pound Chain transfer agent
M.sub.w/ No. (CTA) M.sub.n M.sub.w M.sub.n Yield.sup.1) 2.1
##STR14## 1350 1862 1.38 90% 2.2 ##STR15## 1920 2385 1.24 97% 2.3
##STR16## 1452 1900 1.30 96% 2.4 ##STR17## 1076 1298 1.21 70%
.sup.1)based on the monomer used
EXAMPLE 2
[0158] Oligomers with Monovalent (Hydrophilic) Chain Transfer
Agents: ##STR18##
[0159] a) To a 50 ml round bottomed flask, equipped with mechanical
stirrer, condenser, thermometer, nitrogen inlet and dropping
funnel, 2.59 g of allyl Solketal.RTM., 5 ml of toluene as solvent
and 0.128 g
bis(tricyclopentylphosphine)dichloro(3-methyl-2-butenylidene)ruthenium
(APT Cat ASMC 716) are added at room temperature. A solution of
8.47 g 2-norbornene and 21.53 g
2,2-dimethyl-4-(bicyclo[2.1.1]hepten-(5)-yl-(2)-methoxymethyl)-1,3-dioxol-
ane (90%, preparation described below) are dropped into the flask
and the temperature is maintained for 30 min. at 35-40.degree. C.
The temperature of the reaction mixture is then maintained for 8
hours at 50.degree. C. under stirring.
[0160] The reaction mixture is then transferred into a 500 ml
autoclave containing 100 ml toluene. After rinsing the autoclave
with nitrogen the reaction mixture is hydrogenated for 18 hours at
100.degree. C. under 40 bars of hydrogen pressure. The cooled
reaction mass is filtered through a cake of Tonsil.RTM. 414 FF as
filter aid in a Buchner funnel. The solvent is distilled off under
vacuum and 30 g of a pale, grey wax are obtained. To liberate the
free hydroxy groups the product is dissolved in 200 ml of THF. 1 g
of 6 N HCl solution and 3 g of water are added, and the solution is
left at room temperature overnight. The solution is filtered after
treatment with active charcoal, and the solvent is distilled off
under vacuum. 26 g of a light grey wax are obtained. Softening
range: 110-120.degree. C.; GPC: M.sub.n: 1966, M.sub.w: 3295,
M.sub.w/M.sub.n: 1.68.
[0161] b) The starting material is prepared as follows: Preparation
of
2,2-dimethyl-4-(bicyclo[2.1.1]hepten-(5)-yl-(2)-methoxymethyl)-1,3-dioxol-
ane as Chain Transfer Agent (CTA) ##STR19##
[0162] To a 500 ml autoclave, 40 g of dicyclopentadiene and 130.3 g
of allyl Solketal.RTM. are given at room temperature. After rinsing
with nitrogen the mass is heated and maintained for 16 hours at
150.degree. C. After cooling to room temperature the reaction mass
is distilled under vacuum in a Claisen equipment and 2 fractions
are collected. The second fraction (2 mm Hg, 100-120.degree. C.)
contains 76 g of approximately 90% (GC) of the desired product.
EXAMPLE 3
[0163] Oligomers with Bivalent Chain Transfer Agents ##STR20##
[0164] a) In a 250 ml round bottomed flask, equipped with
mechanical stirrer, condenser, thermometer, nitrogen inlet and
dropping funnel, 12.7 g of diallyl PEG 400 (preparation described
below), 90 ml of toluene as solvent and 0.228 g
bis(tricyclopentylphosphine)dichloro(3-methyl-2-butenylidene)ruthenium
(APT Cat ASMC 716) as catalyst are added at room temperature. A
degassed solution of 30 g of 2-norbornene in 30 ml of toluene is
slowly added within one hour via the dropping funnel. The
temperature is kept under 40.degree. C. After the addition of the
2-norbornene solutions the temperature of the reaction mixture is
maintained for 16 hours at 40.degree. C. under stirring. The
reaction mass is then transferred into an autoclave and
hydrogenated for 18 hours at 100.degree. C. under 15 bars of
hydrogen pressure. The cooled reaction mass is filtered through a
cake of Tonsil.RTM. 414 FF as filter aid in a Buchner funnel. The
solvent is distilled off under vacuum and 38.7 g of a light brown
wax are collected. Softening range: 110-120.degree. C.; GPC:
M.sub.n: 2051, M.sub.w 2972, M.sub.w/M.sub.n: 1.45.
[0165] The oligomer obtained can be represented by the following
general formula ##STR21## n,m: approximately 6; r: approximately
8
[0166] b) Preparation of the starting material Preparation of the
Bivalent Chain Transfer Agent (CTA) ##STR22##
[0167] To a 250 ml round bottom flask, equipped with mechanical
stirrer, condenser, thermometer, nitrogen inlet and dropping
funnel, 30 ml of THF, 60 g of PEG 400 (MW 400) and 12.3 g of NaOH
fine powder are given at room temperature. 63.5 g Allyl bromide (MW
120.98) are slowly added via the dropping funnel. The reaction is
strongly exothermic. The temperature is maintained for two hours at
50-60.degree. C. The reaction mass is cooled to room temperature,
diluted with methylene chloride and washed with water to eliminate
the salts. After evaporating the solvent the residue is distilled
under vacuum and 69 g of viscous yellow oil are obtained (yield:
approx. 95%).
Application Examples
[0168] a) In order to determine the antifog properties of the
tested compound in LDPE films, the compounds are incorporated in
the polymer according to the following procedure:
[0169] Samples from the compounds mentioned in Table 4 are weighed
and added to LDPE pellets [Riblene.RTM. FF 29, Enichem Milano,
Italy; density: 0.921 g/cm.sup.3; melt flow index: 0.6 (190.degree.
C./2.16 kg)] to give a mixture of 1% or 2% by weight of the test
compound. The mixtures are mixed in a turbo mixer and extruded at
the maximum temperature of 200.degree. in an OMC twin-screw
extruder. The granules obtained are press moulded for 3 minutes at
170.degree. C. in a Pasadena press, which produces films of a
thickness of about 150.mu..
[0170] b) Films are evaluated according to the so-called hot fog
test, which consists of immersing 250 ml glass beakers at
60.degree. C. for about 1/2 of their height in a water bath. The
beakers contain about 50 ml of water and on their top the films
that have to be evaluated. The films are observed at defined
intervals from the start of the experiment and a conventional
rating with a range from A to E is assigned, on the basis of the
appearance described in Table 3 below: TABLE-US-00003 TABLE 3
Rating for Hot Fog Tests Perfor- Description mance Rating Comments
An opaque layer of small Fail A No visibility, poor fog droplets
light transmission An opaque layer of large Fail B No visibility,
poor fog droplets light transmission A complete layer of large Poor
C Poor visibility, lens transparent droplets effect, dripping
Randomly scattered large Fair D Discontinuous film transparent
droplets of water Few small or large Good D/E Discontinuous film
transparent droplets of water, mostly transparent A transparent
film dis- Excellent E Completely playing no visible water
transparent
[0171] c) Films containing 1% or 2% of the additives are subjected
to the Hot Fog Test. All films have the rating of A at the
beginning of the experiment. They appear more transparent shortly
afterwards and maintain their quality for a long period of time,
followed by slow decaying. The persistency of performance for
months under hot and wet conditions points to a long-term positive
effect in the event that the films are used in greenhouses. Some
Results are given in Table 4 below (h: hours): TABLE-US-00004 TABLE
4 Hot Fog Test Performance Compound Performance 2.2 (1%) D or
better for 1350 h; between C and D for further 1050 h 2.4 (1%) D or
better for 1000 h; between C and D for further 1400 h 2.4 (2%) D or
better for 2450 h; between C and D for a minimum of further 850 h
Control, no additive From A to B after 30 minutes, no further
change
* * * * *