Process for the production of aqueous polymer dispersions

Details Process for the production of aqueous polymer dispersions Process for the production of aqueous polymer dispersions

2001-12-17

2004-10-05

Yoon, Tae H. (Department: 1714)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C524S804000, C524S836000

Reexamination Certificate

active

06800699

ABSTRACT:

DESCRIPTION
The present invention relates to a process for the production of aqueous polymer dispersions by the reaction of one or more olefinically unsaturated compounds [olefin(s)] in aqueous medium in the presence of
a1) a complex compound of the general formula Ia and/or Ib
in which the substituents and indices have the following meaning:
M a transition metal of groups 7 to 10 of the periodic system of the elements,
L
1
phosphanes (R
16
)
x
PH
3−x
or amines (R
16
)
x
NH
3−x
having identical or different substituents R
16
, ethers (R
16
)
2
O, H
2
O, alcohols (R
16
)OH, pyridine, pyridine derivatives of the formula C
5
H
5−x
(R
16
)
x
N, CO, C
1
-C
12
alkyl nitriles, C
6
-C
14
aryl nitriles or ethylenically unsaturated double-bonded systems, x standing for an integer between 0 and 3,
L
2
halide ions, amide ions (R
16
)
h
NH
2−h
, h standing for an integer between 0 and 2, and furthermore C
1
-C
6
alkyl anions, allyl anions, benzyl anions or aryl anions,
wherein L
1
and L
2
can be linked to one another by means of one or more covalent bonds,
E nitrogen,
Y oxygen, sulfur, N-R
10
or P-R
10
,
R
1
hydrogen, C
1
-C
12
alkyl groups, C
7
-C
13
aralkyl substituents or C
6
-C
14
aryl groups,
R
2
, R
3
independently of one another hydrogen,
C
1
-C
12
alkyl, wherein the alkyl groups can be branched or unbranched,
C
1
-C
12
alkyl, singly or multiply substituted by identical or different C
1
-C
12
alkyl groups, halogens, C
1
-C
12
alkoxy groups or C
1
-C
12
thioether groups,
C
7
-C
13
aralkyl,
C
3
-C
12
cycloalkyl,
C
3
-C
12
cycloalkyl, singly or multiply substituted by identical or different C
1
-C
12
alkyl groups, halogens, C
1
-C
12
alkoxy groups or C
1
-C
12
thioether groups,
C
6
-C
14
aryl,
C
6
-C
14
aryl, identically or differently substituted by one or more C
1
-C
12
alkyl groups, halogens, singly or multiply halogenated C
1
-C
12
alkyl groups, C
1
-C
12
alkoxy groups, silyloxy groups OSiR
11
R
12
R
13
, amino groups NR
14
R
15
or C
1
-C
12
thioether groups,
C
1
-C
12
alkoxy groups,
silyloxy groups OSiR
11
R
12
R
13
,
halogens or
amino groups NR
14
R
15
,
wherein the substituents R
2
and R
3
can form a saturated or unsaturated 5- to 8-membered ring with one another,
R
4
to R
7
independently of one another hydrogen,
C
1
-C
12
alkyl, wherein the alkyl groups can be branched or unbranched,
C
1
-C
12
alkyl, singly or multiply substituted by identical or different C
1
-C
12
alkyl groups, halogens, C
1
-C
12
alkoxy groups or C
1
-C
12
thioether groups,
C
7
-C
13
aralkyl,
C
3
-C
12
cycloalkyl,
C
3
-C
12
cycloalkyl, singly or multiply substituted by identical or different C
1
-C
12
alkyl groups, halogens, C
1
-C
12
alkoxy groups or C
1
-C
12
thioether groups,
C
6
-C
14
aryl,
C
6
-C
14
aryl, identically or differently substituted by one or more C
1
-C
12
alkyl groups, halogens, singly or multiply halogenated C
1
-C
12
alkyl groups, C
1
-C
12
alkoxy groups, silyloxy groups OSiR
11
R
12
R
13
, amino groups NR
14
R
15
or C
1
-C
12
thioether groups,
C
1
-C
12
alkoxy groups,
silyloxy groups OSiR
11
R
12
R
13
,
halogens,
NO
2
groups or
amino groups NR
14
R
15
,
wherein pairs of neighboring substituents R
4
to R
7
can form a saturated or unsaturated 5- to 8-membered ring with one another,
R
8
, R
9
independently of one another in hydrogen,
C
1
-C
6
alkyl groups,
C
7
-C
13
aralkyl substituents or
C
6
-C
14
aryl groups, optionally substituted by one or more C
1
-C
12
alkyl groups, halogens, singly or multiply halogenated C
1
-C
12
alkyl groups, C
1
-C
12
alkoxy groups, silyloxy groups OSiR
11
R
12
R
13
, amino groups NR
14
R
15
or C
1
-C
12
thioether groups,
R
10
to R
15
independently of one another hydrogen,
C
1
-C
20
alkyl groups, which on their part may be substituted by O(C
1
-C
6
alkyl) or N(C
1
-C
6
alkyl)
2
groups,
C
3
-C
12
cycloalkyl groups,
C
7
-C
13
aralkyl substituents or C
6
-C
14
aryl groups,
R
16
hydrogen,
C
1
-C
20
alkyl groups, which for their part may be substituted by O(C
1
-C
6
alkyl) or N(C
1
-C
6
alkyl)
2
groups,
C
3
-C
12
cycloalkyl groups,
C
7
-C
13
aralkyl substituents or C
6
-C
14
aryl groups,
b) dispersing agents and optionally
c) organic solvents having low solubility in water,
d) the metal complexes al) being dissolved in a portion or the total quantity of the olefinically unsaturated compounds and/or of the organic solvents c) having low solubility in water and
e) the portion or the total quantity of the olefinically unsaturated compounds and/or of the organic solvents c) having low solubility in water which hold the metal complexes a1) in solution being present in the aqueous medium as a dispersed phase having an average droplet diameter ≦1,000 nm.
Aqueous polymer dispersions are used commercially in numerous highly diverse applications. Examples which may be mentioned are paper applications (coating and surface sizing), raw materials for surface coatings and paints, adhesives raw materials (including pressure-sensitive adhesives), textile and leather applications, building chemicals, molded foams (mattresses, carpet backings) as well as medical and pharmaceutical products, for example as binding agents for preparations. A summary may be found in D. Distler (editor) “Wässrige Polymerdispersionen [Aqueous polymer dispersions]”, Wiley-VCH Verlag, 1st edition, 1999.
The common processes for the production of aqueous polymer dispersions from the olefins: ethene, propene and/or 1-butene make use of either free-radical high-pressure polymerization or alternatively of the production of secondary dispersions. These processes suffer from disadvantages. The free-radical polymerization process requires extremely high pressures, they are limited on the industrial scale to ethylene and ethylene copolymers and the equipment required is very expensive to procure and maintain (F. Rodriguez, Principles of Polymer Systems, 2nd edition, McGraw-Hill, Singapore 1983, page 384). Another method consists in that first of all the aforesaid olefins are polymerized by any particular process and then a secondary dispersion is prepared, as described by way of example in U.S. Pat. No. 5,574,091. This method is a multistage process and hence very expensive.
It was, accordingly, desirable to produce aqueous polymer dispersions from olefins, such as the olefins ethylene, propylene, butylene, etc., available on an industrial scale in one process step by polymerization of the olefins in aqueous medium. In addition, polymerization in aqueous medium quite generally has the advantage that it is simple to dissipate the heat of polymerization due to the nature of the process. Finally, polymerization reactions in aqueous systems are quite generally of interest simply because water is an inexpensive and environmentally friendly solvent.
The following state of the art forms the starting point for the metal-complex catalyzed polymerization of olefins.
Olefins can be polymerized using electrophilic transition metal compounds such as TiCl
4
(Ziegler-Natta catalyst) or metallocenes as described by way of example by H.-H. Brintzinger et al. in
Angew. Chem
. 1995, 107, pages 1255 et seq. and
Angew. Chem., Int. Ed. Engl
. 1995, 34, pages 1143 et seq. However, both TiCl
4
and metallocene are sensitive to moisture and are, therefore, not very suitable for the polymerization of olefins in aqueous medium. The aluminum alkyls employed as cocatalysts are also sensitive to moisture so that water as an anticatalyst must be carefully excluded.
There are just a few reports on transition-metal catalyzed reactions of olefins, such as ethylene for example, in aqueous conditions. Thus, L. Wang et al. in
J. Am. Chew. Soc
. 1993, 115, pages 6999 et seq. report on a rhodium-catalyzed polymerization. With about one insertion/hour, however, the activity is much too low for industrial applications.
The reaction of ethylene with nickel P, O-chelate complexes as described in the US specifications U.S. Pat. Nos. 3,635,937, 3,637,636, 3,661,803 and 3,686,159 appears distinctly promising. It is disadvant

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