Stabilized halogen-containing polymers

Details Stabilized halogen-containing polymers Stabilized halogen-containing polymers

1997-02-12

2003-03-11

Szekely, Peter (Department: 1714)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

At least one aryl ring which is part of a fused or bridged...

C524S399000, C524S178000, C524S179000, C524S180000, C524S181000, C524S182000

Reexamination Certificate

active

06531533

ABSTRACT:

The present invention relates to stabilised halogen-containing polymers or recyclates thereof, preferably polyvinyl chloride (PVC) or recyclates thereof, and to a stabiliser mixture comprising specific zeolites, metal soaps and/or organotin compounds, as well as to a process for the preparation of stabilised halogen-containing polymers.
In addition to tin and lead compounds, PVC is also stabilised using fatty acid salts (so-called metal soaps), where the metals are usually barium, cadmium, zinc, magnesium, calcium or, once more, lead. In view of the different stabilisation properties (initial colour, colour retention and long-term stability), a combination of two different metals soaps, for example barium/cadmium soaps, is used to achieve a balanced stabilisation. In order to avoid the use of compounds containing barium, lead or cadmium, the use of calcium/zinc soaps has also been proposed; cf for example “Taschenbuch der Kunststoff-Additive”, edited by R. Gächter and H. Müller, (hereinafter abbreviated to “KA'e G & M”) Hanser Verlag, 3rd Edition, 1990, pages 308-309, and “Kunststoff Handbuch PVC”, Volumes 1 and 2, Beck/Braun, Carl Hanser Verlag, 2nd Edition, 1985/1986.
It has also been proposed, inter alia, to use, as costabiliser for PVC, a compound of the series of the zeolites or hydrotalcites; examples are given in EP-A-0 062 813, EP-A-0 432 495, U.S. Pat. No. 5,216,058 as well as in U.S. Pat. No. 4,000,100, where the use of non-activated zeolite A is disclosed.
Efforts continue to provide physiologically acceptable stabiliser systems which at the same time are capable of providing high stabilisation. Stabiliser systems which are to be avoided in particular are those containing barium, lead or cadmium.
It has now been found that specific zeolites may be combined surprisingly well, in particular with metal soaps and/or organotin compounds such that a halogen-containing polymer is provided with excellent long-term stability while having good initial colour and colour retention. Surprisingly, PVC stabilised according to this invention has e.g. markedly enhanced transparency and colour retention as compared to PVC stabilised in conventional manner.
Accordingly, the invention relates to compositions comprising
(a) a halogen-containing polymer or the recyclate thereof;
(b) at least one zeolite in the form of alkali, preferably in the form of sodium, potasssium and/or lithium, in particular at least one zeolite of formula
M
2
O.Al
2
O
3
.x
SiO
2
.y
H
2
O  (I),
wherein M is Na, K or Li, x is 2 to 12, and y is 1 to 15, preferably Na
2
O.Al
2
O
3
.(2 to 5)SiO
2
.(3.5 to 10) H
2
O (zeolite P or zeolite MAP or MA-P), with the exception of zeolite A, Na
12
Al
12
Si
12
O
48
.27 H
2
O and clinoptilolite Na
6
Al
6
Si
30
O
72
.2 H
2
O,
(c) at least one organic zinc, aluminium or rare earth compound, preferably at least one metal soap, and/or
(d) at least one organotin compound of one of the formulae I to VII
[R
1
]
i
Sn[—Q—R
2
]
4−i
  (I),
 R
p
SnS
q
  (VI)
and
[R
p
SnS
q
]
r
  (VII),
 wherein
R and R
1
are each independently of the other C
1
-C
12
alkyl or C
3
-C
11
alkoxycarbonylethyl,
Q has the meaning of —S— or —O—CO—, and
R
2
, if Q is —S—, is C
8
-C
18
alkyl or a —R
3
—COO—R
4
or —R
3
—O—CO—R
4
radical,
R
2
, if Q is —O—CO—, is C
1
-C
18
alkyl, C
2
-C
18
alkenyl, phenyl, C
1
-C
4
alkyl-substituted phenyl, or a —CH═CH—COO—R
5
radical,
R
3
is methylene, ethylene or o-phenylene,
R
4
is C
5
-C
18
alkyl,
R
5
is C
1
-C
18
alkyl, C
5
-C
7
cycloalkyl or benzyl,
R
6
, if Q is —S—, is methylene, ethylene or o-phenylene,
R
6
, if Q is —O—CO—, is C
1
-C
8
alkylene, o-phenylene or a —CH═CH— group,
R
7
is C
2
-C
4
alkylene or C
4
-C
8
alkylene which is interrupted by —O—,
R
8
is C
1
-C
18
alkyl, C
2
-C
18
alkenyl, phenyl, C
1
-C
4
alkyl-substituted phenyl, or a —CH═CH—COO—R
5
radical,
X independently has the meaning of —O— or —O—CO—R
9
—COO—,
R
9
is C
1
-C
8
alkylene, o-phenylene or a —CH═CH— group,
p is 1 or 2, q is [(4−p)/2], and r>1,
i is 1 or 2, j is a number in the range from 1 to 6, k is a number in the range from 1 to 3, and m is a number in the range from 1 to 4.
The abbreviated form —COO— used above, throughout the description and in the claims denotes the grouping
and —O—CO— denotes the grouping
R
1
, R
2
, R
4
, R
5
and R
8
defined as alkyl are, within the scope of the indicated number of carbon atoms, typically methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
Isooctyl denotes the alkyl radicals of the mixture originating from the oxo process and consisting of primary branched alcohols R′CH
2
OH, wherein R′ is a branched heptyl group (Merck Index 10th Ed., 5041).
R defined as alkyl is preferably n- and isoalkyl radicals, particularly preferably methyl, ethyl and n-butyl.
R
1
defined as alkyl is preferably methyl, butyl or octyl. R
1
defined as C
3
-C
11
alkoxycarbonylethyl is C
1
-C
8
alkyl-O—CO—CH
2
—CH
2
—.
R
2
and R
8
defined as C
2
-C
18
alkenyl are, inter alia, ethenyl (vinyl), propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-heptadec-8-enyl, n-octadec-2-enyl, n-octadec-4-enyl.
R
2
and R
8
defined as C
1
-C
4
alkyl-substituted phenyl typically embraces methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl.
R
2
, R
6
, R
8
and R
9
defined as —CH═CH—COO—R
5
or —CH═CH— are derived from maleic acid or fumaric acid, preferably from maleic acid.
R
5
defined as C
5
-C
7
cycloalkyl ist cyclopentyl, cyclohexyl or cycloheptyl, preferably cyclopentyl or cyclohexyl and, most preferably, cyclohexyl.
R
6
and R
7
defined as alkylene is a divalent alkyl radical; within the scope of the indicated chain lengths R
6
and R
7
are typically methylene, ethylene, —CH(CH
3
)—CH
2
—, —(CH
2
)
3
—, —(CH
2
)
4
—, —(CH
2
)
6
—, —(CH
2
)
8
—, —CH
2
—CH(C
2
H
5
)—(CH
2
)
4
—, —CH
2
—C(CH
3
)
2
—CH
2
—; straight-chain radicals being preferred. R
7
is C
4
-C
8
alkylene which is interrupted by —O—, typically —(CH
2
)
2
—O—(CH
2
)
2
—, —(CH
2
)
3
—O—(CH
2
)
3
, —(CH
2
)
2
—O—(CH
2
)
4
— or —(CH
2
)
4
—O—(CH
2
)
4
—, preferably —(CH
2
)
2
—O—(CH
2
)
2
—. The unit (O—CH
2
—CH
2
) can also be present several times. Typical examples of such radicals are (CH
2
)
2
—(O—CH
2
CH
2
—)
2
— and —(CH
2
)
2
—(O—CH
2
CH
2
—)
3
.
Component (a)
Preferred halogen-containing polymers or their recyclates are those which contain chlorine, typically polymers of vinyl chloride and vinylidene chloride, vinyl resins containing vinyl chloride units in their structure, e.g. copolymers of vinyl chloride and vinyl esters of aliphatic acids, in particular vinyl acetate; copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile; copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or anhydrides thereof, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride; post-chlorinated polymers and copolymers of vinyl chloride; copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others, such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like; polymers of vinylidene chloride and copolymers thereof with vinyl chloride and other polymerisable compounds; polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and alpha-substituted acrylic acid; polymers of chlorinated styrenes, for example dichlorostyrene; chlorinated rubbers; chlorinated polymers of ethylene; polymers and post-chlorinated polymers of chlorobutadiene and copolymers thereof with vinyl chloride, rubber hydrochloride and chlor

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