Phosphorus compounds

Details Phosphorus compounds Phosphorus compounds

1995-09-28

2002-04-09

Hoke, Veronica P. (Department: 1714)

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

Synthetic resins

Processes of preparing a desired or intentional composition...

Reexamination Certificate

active

06369140

ABSTRACT:

This invention relates to the use of certain phosphorus-containing compounds that can act at low concentrations as stabilizers for polyolefins against degradation caused by heat, mechanical stress or light. They are especially suitable for polyolefins which have been made with a 11 and higher generation catalyst (e.g. II to V generation catalysts).
According to the invention, there is provided a polyolefinic composition comprising:
a) a compound of formula I to III
 in which
each R
1
independently is selected from linear or branched C
1-30
alkyl, C
5-12
cycloalkyl, C
2-24
alkenyl, C
2-18
alkoxyalkyl, C
2-19
alkanoylmethylene, C
7-30
alkaryl, C
7-30
aralkyl, C
4-24
heteroaryl where any one of the above substituents of R
1
are unsubstituted or are substituted by 1 to 3 groups selected from C
1-12
alkyl, —OR
4
, —NR
4
R
5
, —COR
4
and —COOR
4
); and C
6-30
aryl, unsubstituted or substituted by 1 to 5 groups R
3
selected from C
1-12
alkyl, C
18
alkoxy, C
5-6
cycloalkyl, phenyl or phenoxy, —OR
4
, —NR
4
R
5
, —COR
4
and —COOR
4
,
R
4
and R
5
independently are selected from hydrogen, C
1-30
alkyl (linear or branched), C
5-12
cycloalkyl, C
6-24
aryl, C
7-30
alkaryl or C
7-30
aralkyl;
A is a direct bond, a group —(P—R
1
)
p
— or an n-valent aliphatic or aromatic residue, preferably C
1-30
alkylene (linear or branched), C
5-12
cycloalkylene, C
7-30
alkarylene, C
7-30
aralkylene, C
6-24
arylene, a N—, O—, S—, or P— containing C
6-24
heteroarylene, C
2-30
alkylidene or C
2-30
alkylene interrupted by N, O or S;
m is 3 to 12 preferably 4-6;
n is 2 to 5; and
p is 1 to 12; preferably 1-5;
(the compounds of formulae I to III hereinafter being called “component a”); and
b) a polyolefin which has been produced in the presence of a Ziegler or metallocene type catalyst which has not been removed (hereinafter called “component b”).
For the avoidance of doubt, compounds of formula III are cyclic compounds.
In the compounds of Formula I, when n is 2 and A is C
1-3
alkylene, A in such a case is preferably —CH
2
— or C
5-30
alkylene.
Preferred compounds of formula I are of formula Ia
(R
1
′)
3
P  (Ia)
in which
each R
1
′ independently is selected from C
8-18
alkyl, C
6-18
aryl, C
4-12
heteroaryl, C
2-18
alkoxyalkyl, C
7-30
alkaryl, C
7-30
aralkyl, C
2-19
alkanoylmethylene, or a group of formula &ggr;
in which
each R
3
is independently selected from C
1-8
alkyl, C
1-8
alkoxy, C
5-6
cycloalkyl, phenyl or phenoxy; and
q is 1 to 5; preferably from 1 to 3.
Preferred compounds of formula II are of formula IIa
A′—(P(R
1
′)
2
)
n′
  (IIa)
in which
each R
1
′ independently is selected from C
8-18
alkyl, C
6-18
aryl, C
4-12
heteroaryl, C
2-18
alkoxyalkyl, C
7-30
alkaryl, C
7-30
aralkyl, C
2-19
alkanoylmethylene or a group of formula &ggr;
in which
each R
3
is independently selected from C
1-8
alkyl, C
1-8
alkoxy, C
5-6
cycloalkyl, phenyl or phenoxy; and
q is 1 to 5; preferably from 1 to 3; and
A′ is selected from C
1-12
alkylene, C
1-12
alkylidene, C
6-18
arylene, C
4-12
heteroarylene, C
5-12
alkylene, C
12-18
cycloalkylene, phenoxyphenylene, C
3-18
alkylaminoC
1-12
alkylene; and
n′ is 2 to 4.
Preferred compounds of formula III are of formula IIIa
>(P—R
2
′)
m′
  (IIIa)
in which
each R
2
′ independently is C
1-12
alkyl, cyclohexyl, methyl or C
6-12
aryl; and m′ is 4 or 5.
More preferred compounds of formula I are of formula Ib
(R
1
″)
3
P  (Ib)
in which
each R
1
″ independently is selected from C
10-18
alkyl, C
6-12
aryl, C
4-10
heteroaryl, C
3-18
alkoxyalkyl, C
2-19
alkanoylmethylene, C
7-24
alkaryl, C
7-24
aralkyl, or a group of formula &ggr;
in which
each R
3
is independently selected from C
1-8
alkyl, C
1-8
alkoxy, C
5-6
cycloalkyl, phenyl or phenoxy; and
q is 1 to 5; preferably from 1 to 3.
More preferred compounds of formula II are of formula IIb
A″—(P—(R
1
′″)
2
)
n″
  IIb
in which
each R
1
′″ independently is selected from C
10-18
alkyl, C
4-9
heteroaryl, C
7-24
alkaryl, C
4-18
alkoxyalkyl or of formula &ggr;
in which
each R
3
is independently selected from C
1-8
alkyl, C
1-8
alkoxy, C
5-6
cycloalkyl, phenyl or phenoxy; and
q is 1 to 5; preferably from 1 to 3;
A′ is selected from C
2-12
alkylene, C
2-12
alkylidene, C
6-12
arylene, C
2-12
alkoxyalkyle phenoxyphenylene, C
4-10
heteroarylene, C
6-8
cycloalkylene, C
3-12
alkylaminoalkylene; and
n″ is 2 to 4.
Most preferred are of formula I are of formula Ic
(R
1
′″)
3
P  (Ic)
in which
each R
1
′″ independently is selected from C
10-18
alkyl, C
4-9
heteroaryl, C
7-24
alkaryl, C
4-18
alkoxyalkyl or of formula &ggr;
in which
each R
3
is independently selected from C
1-8
alkyl, C
1-8
alkoxy, C
5-6
cycloalkyl, phenyl or phenoxy; and
q is 1 to 5; preferably from 1 to 3.
Most preferred compounds of formula II are of formula IIc
A′″—(P—(R
1
′″)
2
)
n′″
  (IIc)
in which R
1
′″ is as defined above;
A′″ is selected from C
5-12
alkylene, C
6-12
arylene, C
4-12
alkoxyalkylene, phenoxyphenylene, C
4-9
heteroarylene, cyclohexylene, cyclooctylene, C
3-8
alkyl-aminoalkylene; and
n′″ is 2 or 3.
The compounds of formulae I to III may be made from known compounds by known methods. Reviews of such reaction procedures are given in e.g. G. M. Kosolapoff, Organic Phosphorus Compounds, Vol. 1-7, Wiley, New York, 1972 or Houben/Weyl, Methoden der Organischen Chemie, Vol. 12, 4. Auflage, Georg Thieme Verlag, Stuttgart 1963 and corresponding supplementary volumes. The contents of which are incorporated herein by reference.
Compounds of Formula II wherein A is a direct bond and compounds of Formula III are also prepared by a process which comprises reacting either a secondary phosphine of the formula R
1
R
1
PH or a primary phosphine of the formula R
1
PH
2
with a halogen, preferably chlorine or bromine, in the presence of an acid acceptor, for example, an oxide, hydroxide, or carbonate of an alkali or alkaline earth metal or an amine, preferably a tertiary amine, optionally in the presence of an inert solvent. Secondary phosphines result in compounds of Formula II wherein A is a direct bond. Primary phosphines result in compounds of Formula III. Advantageously, this process uses as starting materials alkyl phosphines which are more readily available than the halophosphines that are used in the art.
Typically those compounds are prepared from organohalides such as alkyl- or aryl chlorides or alkyl or arylbromides and PCl
3
via a Grignard or modified Wurtz reaction; via Friedel-Crafts reaction; by addition of P—H containing compound to multiple bonds; by Arbuzov reaction of diorganophosphinites with organohalides and subsequent reductions; or by derivation from already formed phosphines.
Compounds of formula I to III of special interest are selected from:
Tris-octyl-phosphine
Tris-decyl-phosphine
Tris-dodecyl-phosphine
Tris-tetradecyl-phosphine
Tris-hexadecyl-phosphine
Tris-octadecyl-phosphine
Tris-benzyl-phosphine
Phenyl-dibenzyl-phosphine
Diphenyl-benzyl-phosphine
Tris(1-phenylethyl)phosphine
Phenyl-di(1-phenylethyl)phosphine
Diphenyl-(1-phenylethyl)phosphine
Tris(2-phenylethyl)phosphine
Phenyl-di(2-phenylethyl)phosphine
Diphenyl(2-phenylethyl)phosphine
Tris(2-phenyl-2-methylethyl)phosphine
Phenyl-di(2-phenyl-2-methylethyl)phosphine
Diphenyl(2-phenyl-2-methylethyl)phosphine
Tris(2-methyl-phenyl)phosphine
Tris(4-methyl-phenyl)phosphine
Tris(2-ethyl-phenyl)phosphine
Tris(4-methyl-phenyl)phosphine
Tris(2-tert-butyl-phenyl)phosphine
Tris(4-tert-butyl-phenyl)phosphine
Tris(2-butyl-phenyl)phosphine
Tris(4-butyl-phenyl)phosphine
Tris(2-octyl-phenyl)phosphine
Tris(4-octyl-phenyl)phosphine
Tris(2,4-dimethyl-phenyl)phosphine
Tris(2,6-dimethyl-phenyl)phosphine
Tris(2,4-diethyl-phenyl)phosphine
Tris(2,6-diethyl-phenyl)phosphine
Tris(2,4,6-trimethyl-phenyl)phosphine
Tris(2,4,6-triethyl-phenyl)phosphine
Tris(2,4-di-tert-butyl-phenyl)phosphine
Tris(2,6-di-tert-butyl-phenyl)phosphine

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