U.S. patent application number 12/060503 was filed with the patent office on 2008-07-31 for method for emulsion polymerisation of olefins.
This patent application is currently assigned to BASF Aktiengesellschaft. Invention is credited to Mubarik Mahmood Chowdhry, Monica Haag, Ludmila Kolb, Stefan Mecking, Xavier Sava, Jacob Wildeson.
Application Number | 20080182915 12/060503 |
Document ID | / |
Family ID | 34585164 |
Filed Date | 2008-07-31 |
United States Patent
Application |
20080182915 |
Kind Code |
A1 |
Chowdhry; Mubarik Mahmood ;
et al. |
July 31, 2008 |
METHOD FOR EMULSION POLYMERISATION OF OLEFINS
Abstract
Process for the emulsion polymerization of one or more olefins
by preparing a catalyst by reacting a quinoid compound with a metal
compound and a phosphine compound which is substituted by at least
one polar radical; and subsequently (co)polymerizing said one or
more olefins in water or in a solvent mixture which contains at
least 50% by weight of water and at least one emulsifier.
Inventors: |
Chowdhry; Mubarik Mahmood;
(Strasbourg, FR) ; Sava; Xavier; (Mannheim,
DE) ; Haag; Monica; (Ludwigshafen, DE) ;
Wildeson; Jacob; (Ludwigshafen, DE) ; Mecking;
Stefan; (Freiburg, DE) ; Kolb; Ludmila; (Lahr,
DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
BASF Aktiengesellschaft
Ludwigshafen
DE
|
Family ID: |
34585164 |
Appl. No.: |
12/060503 |
Filed: |
April 1, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10579098 |
May 12, 2006 |
|
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PCT/EP04/12597 |
Nov 6, 2004 |
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12060503 |
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Current U.S.
Class: |
521/65 ;
514/772.3; 524/570; 526/91; 526/93 |
Current CPC
Class: |
C08F 110/02 20130101;
C08F 2/22 20130101; C08F 4/80 20130101; C08F 110/02 20130101; C08F
110/02 20130101 |
Class at
Publication: |
521/65 ; 524/570;
526/91; 526/93; 514/772.3 |
International
Class: |
C08J 9/28 20060101
C08J009/28; C08F 4/42 20060101 C08F004/42; A61K 47/30 20060101
A61K047/30 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 14, 2003 |
DE |
103 53 558.6 |
Claims
1: An aqueous polymer dispersion obtainable by a process
comprising: preparing a catalyst by reacting a quinoid compound of
the formula Ia or Ib or a mixture of at least two of the compounds
Ia or Ib ##STR00009## where R in each case is one or more of the
following radicals: hydrogen, halogen, a nitrile, a
C.sub.1-C.sub.12-alkyl group, a C.sub.1-C.sub.12-alkoxy group, a
C.sub.7-C.sub.15-aralkyl group, a C.sub.6-C.sub.14-aryl group,
unsubstituted or substituted by: C.sub.1-C.sub.12-alkyl groups,
halogens, C.sub.1-C.sub.12-alkoxy groups,
C.sub.3-C.sub.12-cycloalkyl groups, C.sub.1-C.sub.12-thioether
groups, optionally carboxyl groups or sulfo groups present in the
form of their salts, and amino groups with hydrogen and/or
C.sub.1-C.sub.12-alkyl radicals; amino groups NR.sup.1R.sup.2,
where R.sup.1 and R.sup.2 together or separately are hydrogen,
C.sub.1-C.sub.12-alkyl groups, C.sub.7-C.sub.15-aralkyl radicals
and C.sub.6-C.sub.14-aryl groups and optionally additionally form a
saturated or unsaturated 5- to 10-membered ring, unsubstituted or
substituted by: C.sub.1-C.sub.12-alkyl groups, halogens,
C.sub.1-C.sub.12-alkoxy groups, C.sub.3-C.sub.12-cycloalkyl groups,
C.sub.1-C.sub.12-thioether groups, optionally carboxyl groups or
sulfo groups present in the form of their salts, and amino groups
with hydrogen and/or C.sub.1-C.sub.12-alkyl radicals, wherein
identical or different compounds of the formulae Ia and Ib, are
optionally bridged by one or more C.sub.1-C.sub.12-alkylene
bridges, C.sub.2-C.sub.12-alkylated azo bridges or bridges of the
formula II ##STR00010## wherein Y is silicon or germanium and
R.sup.3 and R.sup.4 are hydrogen and/or a C.sub.1-C.sub.12-alkyl
group; with a phosphine compound which is a compound III of the
formula (R').sub.aPH.sub.3-a, wherein a is 1, 2 or 3; R' is a
C.sub.1-C.sub.12-alkyl group, C.sub.3-C.sub.12-cycloalkyl group,
C.sub.7-C.sub.15-aralkyl group or C.sub.6-C.sub.14-aryl group,
which is substituted by at least one polar radical selected from
the group consisting of hydroxyl, carboxyl, sulfo,
hydroxysulfonyloxy or phosphono groups and the alkali metal,
alkaline earth metal and/or ammonium salts thereof,
alkanolammonium, pryidinium, imidazolinium, oxazolinium,
morpholinium, thiazolinium, quinolinium, isoquinolinium, tropylium,
sulfonium, guanidinium and phosphonium groups and ammonium groups
of the formula IV --N(R.sup.7R.sup.8R.sup.9 (IV), where R.sup.7,
R.sup.3 and R.sup.9, independently of one another, are hydrogen or
a C.sub.1-C.sub.12-alkyl group; or a group of the formula V, VI or
VII -(EO).sub.k--(PO).sub.l--R.sup.10 V,
-(PO).sub.l-(EO).sub.k--R.sup.10 VI,
-(EO.sub.k/(PO.sub.l)--R.sup.10 VII; where EO is a
--CH.sub.2--CH.sub.2--O-- group, PO is a
--CH.sub.2--CH(CH.sub.3)--O-- or a --CH(CH.sub.3)--CH.sub.2--O--
group, k and l are numerical values from 0 to 50, but k and l are
not simultaneously 0, R.sup.10 is hydrogen, a
C.sub.1-C.sub.12-alkyl group or a sulfo group or an alkali metal,
alkaline earth metal and/or ammonium salt thereof, and/or a
diphosphine compound VII of the formula
(R').sub.bPH.sub.2-b-G-PR.sub.2'', where R'' is hydrogen or has the
same meaning as R', G is a C.sub.1-C.sub.12-alkylene group,
C.sub.3-C.sub.12-cycloalkylene group, C.sub.7-C.sub.15-aralkylene
group or C.sub.6-C.sub.14-arylene group, and b is 1 or 2; and with
a metal compound of the formula M(L.sup.2).sub.2,
M(L.sup.2).sub.2(L.sup.1).sub.z1, or M(L.sup.1).sub.z2, wherein M
is a transition metal of groups 7 to 10 of the Periodic Table of
the Elements; L.sup.1 is a phosphane (R.sup.5).sub.xPH.sub.3-x or
amine (R.sup.5).sub.xNH.sub.3-x having identical or different
radicals R.sup.5, an ether (R.sup.5).sub.2O, water, an alcohol
(R.sup.5)OH, pyridine, a pyridine derivative of the formula
C.sub.5H.sub.5-x)(R.sup.5).sub.xN, carbon monoxide,
C.sub.1-C.sub.12-alkylnitrile, C.sub.6-C.sub.14-arylnitrile or an
ethylenically unsaturated double bond system, where x is an integer
ranging from 0 to 3; R.sup.5 is hydrogen, a C.sub.1-C.sub.12-alkyl
group, which in turn may be substituted by O(C.sub.1-C.sub.6-alkyl)
or N--(C.sub.1-C.sub.6-alkyl).sub.2 groups; a
C.sub.3-C.sub.12-cycloalkyl group, a C.sub.7-C.sub.15-aralkyl
radical or a C.sub.6-C.sub.14-aryl group, L.sup.2 is a halide ion,
an amide anion (R.sup.6).sub.yNH.sub.2-y--, where y is an integer
ranging from 0 to 2 and R.sup.6 is a C.sub.1-C.sub.12-alkyl group,
and furthermore a C.sub.1-C.sub.6-alkyl anion, allyl anion, benzyl
anion or aryl anion, where L.sup.1 and L.sup.2 may be linked to one
another by one or more covalent bonds; z1 is an integer ranging
from 1 to 4; and z2 is an integer ranging from 1 to 6; and
subsequently (co)polymerizing at least one olefin in the presence
of the prepared catalyst in water or in a solvent mixture which
contains at least 50% by weight of water, in the presence of an
emulsifier.
2: A method of producing paper, textile or leather products,
comprising: in the steps of preparing said paper, textile or
leather product, employing the aqueous polymer dispersion according
to claim 1 in the process of production.
3: A method of producing molding foams, carpet backing coatings and
pharmaceutical formulations, comprising: in the steps of preparing
said molding foams, carpet backing coatings and pharmaceutical
formulations, employing the aqueous polymer dispersion according to
claim 1 in the process of production.
4: A method of producing adhesives, sealing compounds, plastics
renders, coating materials and paints, comprising: in the steps of
preparing said molding foams, carpet backing coatings and
pharmaceutical formulations, incorporating the aqueous polymer
dispersion according to claim 1 as a component of each
material.
5: A polymer powder prepared from an aqueous polymer dispersion
according to claim 1.
Description
[0001] The present invention relates to a process for the emulsion
polymerization of one or more olefins by reacting a quinoid
compound of the formula Ia or Ib or a mixture of at least two of
the compounds Ia or Ib
##STR00001##
[0002] where R in each case is one or more of the following
radicals:
[0003] hydrogen
[0004] halogen
[0005] nitrile
[0006] C.sub.1-C.sub.12-alkyl groups, C.sub.1-C.sub.12-alkoxy
groups, C.sub.7-C.sub.15-aralkyl groups, C.sub.6-C.sub.14-aryl
groups, unsubstituted or substituted by: C.sub.1-C.sub.12-alkyl
groups, halogens, C.sub.1-C.sub.12-alkoxy groups,
C.sub.3-C.sub.12-cycloalkyl groups, C.sub.1-C.sub.12-thioether
groups, if appropriate also carboxyl groups or sulfo groups present
in the form of their salts, and amino groups with hydrogen and/or
C.sub.1-C.sub.12-alkyl radicals, [0007] amino groups
NR.sup.1R.sup.2, where R.sup.1 and R.sup.2 together or separately
are hydrogen, C.sub.1-C.sub.12-alkyl groups,
C.sub.7-C.sub.15-aralkyl radicals and C.sub.6-C.sub.14-aryl groups
and may additionally also form a saturated or unsaturated 5- to
10-membered ring, unsubstituted or substituted by:
C.sub.1-C.sub.12-alkyl groups, halogens, C.sub.1-C.sub.12-alkoxy
groups, C.sub.3-C.sub.12-cycloalkyl groups,
C.sub.1-C.sub.12-thioether groups, if appropriate also carboxyl
groups or sulfo groups present in the form of their salts, and
amino groups with hydrogen and/or C.sub.1-C.sub.12-alkyl
radicals,
[0008] it being possible for identical or different compounds of
the formulae Ia and Ib if appropriate also to be bridged by one or
more C.sub.1-C.sub.12-alkylene bridges, C.sub.2-C.sub.12-alkylated
azo bridges or bridges of the formula II
##STR00002##
[0009] where Y is silicon or germanium and R.sup.3 and R.sup.4 are
hydrogen and/or a C.sub.1-C.sub.12-alkyl group,
[0010] with a phosphine compound,
[0011] and with a metal compound of the formula M(L.sup.2).sub.2,
M(L.sup.2).sub.2(L.sup.1).sub.z, or M(L.sup.1), 2,
[0012] where [0013] M is a transition metal of groups 7 to 10 of
the Periodic Table of the Elements, [0014] L.sup.1 is a phosphane
(R.sup.5).sub.xPH.sub.3-x or amine (R.sup.5).sub.xNH.sub.3-x having
identical or different radicals R.sup.5, an ether (R.sup.5).sub.2O,
water, an alcohol (R.sup.5)OH, pyridine, a pyridine derivative of
the formula C.sub.5H.sub.5)(R.sup.5).sub.xN, carbon monoxide,
C.sub.1-C.sub.12-alkylnitrile, C.sub.6-C.sub.14-arylnitrile or an
ethylenically unsaturated double bond system, where x is an integer
from 0 to 3, [0015] R.sup.5 is hydrogen, a C.sub.1-C.sub.12-alkyl
group, which in turn may be substituted by O(C.sub.1-C.sub.6-alkyl)
or N--(C.sub.1-C.sub.6-alkyl).sub.2 groups, a
C.sub.3-C.sub.12-cycloalkyl group, a C.sub.7-C.sub.15-aralkyl
radical or a C.sub.6-C.sub.14-aryl group, [0016] L.sup.2 is a
halide ion, an amide anion (R.sup.6).sub.yNH.sup..crclbar..sub.2-y,
where y is an integer from 0 to 2 and R.sup.5 is a
C.sub.1-C.sub.12-alkyl group, and furthermore a
C.sub.1-C.sub.6-alkyl anion, allyl anion, benzyl anion or aryl
anion, where L.sup.1 and L.sup.2 may be linked to one another by
one or more covalent bonds, [0017] z1 is an integer from 1 to 4,
and [0018] z2 is an integer from 1 to 6,
[0019] and subsequently using the reaction product for the
polymerization or copolymerization of olefins in water or in a
solvent mixture which contains at least 50% by weight of water, in
the presence of an emulsifier and optionally in the presence of an
activator,
[0020] wherein the phosphine compound used is either a compound III
of the formula (R').sub.aPH.sub.3-a, where R' is a
C.sub.1-C.sub.12-alkyl group, C.sub.3-C.sub.12-cycloalkyl group,
C.sub.7-C.sub.15-aralkyl group or C.sub.6-C.sub.14-aryl group,
which is substituted by at least one polar radical P, the polar
radical P being selected from the group consisting of [0021]
hydroxyl, carboxyl, sulfo, hydroxysulfonyloxy or phosphono groups
and the possible alkali metal, alkaline earth metal and/or ammonium
salts thereof, [0022] alkanolammonium, pyridinium, imidazolinium,
oxazolinium, morpholinium, thiazolinium, quinolinium,
isoquinolinium, tropylium, sulfonium, guanidinium and phosphonium
groups and ammonium groups of the formula IV [0023]
--N.sup..sym.R.sup.7R.sup.8R.sup.9 IV, where [0024] R.sup.7,
R.sup.3 and R.sup.9, independently of one another, are hydrogen or
a C.sub.1-C.sub.12-alkyl group, [0025] or [0026] a group of the
formula V, VI or VII [0027] -(EO).sub.k--(PO).sub.l--R.sup.10 V,
[0028] -(PO).sub.l-(EO).sub.k--R.sup.10 VI, [0029]
-(EO).sub.k/PO.sub.l)--R.sup.10 VII, where [0030] EO is a
--CH.sub.2--CH.sub.2--O-- group, [0031] PO is a
--CH.sub.2--CH(CH.sub.3)--O-- or a --CH(CH.sub.3)--CH.sub.2--O--
group, [0032] k and l are numerical values from 0 to 50, but k and
l are not simultaneously 0, [0033] R.sup.10 is hydrogen, a
C.sub.1-C.sub.12-alkyl group or a sulfo group or the corresponding
alkali metal, alkaline earth metal and/or ammonium salt thereof,
and
[0034] a is 1, 2 or 3,
[0035] and/or a diphosphine compound VIII of the formula
(R').sub.bPH.sub.2-b-G-PR.sub.2'', where R'' is hydrogen or has the
same meaning as R', G is a C.sub.1-C.sub.12-alkylene group,
C.sub.3-C.sub.12-cycloalkylene group, C.sub.7-C.sub.15-aralkylene
group or C.sub.6-C.sub.14-arylene group, and
[0036] b is 1 or 2.
[0037] Isolation and purification of the complex formed in situ
(reaction product of metal compound, phosphine compound and quinoid
compound) are dispensed with.
[0038] An activator is optionally used for the novel process.
Furthermore, this invention relates to dispersions of polyolefins,
for example polyethylene and ethylene copolymers in water, and the
use of the novel aqueous dispersions in paper applications and
textile and leather applications, for the production of molded
foams, carpet backing coatings and pharmaceutical formulations and
as a component in adhesives, sealing compounds, plastics renders,
coating materials and paints.
[0039] Aqueous dispersions of polymers are utilized commercially in
numerous applications which differ very greatly. Examples are paper
applications (coating and surface sizing), raw materials for paints
and finishes, adhesive raw materials (including contact adhesives),
textile and leather applications, in construction chemistry, molded
foams (mattresses, carpet backing coatings) and for medical and
pharmaceutical products, for example as binders for preparations. A
summary is to be found in D. Distler (Editor), Wa.beta.rige
Polymerdispersionen, Wiley-VCH Verlag, 1st Edition, 1999.
[0040] It has been difficult to date to prepare aqueous dispersions
of polyolefins. However, it would be desirable to be able to
provide such aqueous dispersions of polyolefins because the
monomers, such as ethylene or propylene, are very advantageous from
economic points of view.
[0041] The conventional process for the preparation of such aqueous
dispersions from corresponding olefins make use either of free
radical high-pressure polymerization or of the preparation of
secondary dispersions.
[0042] These processes therefore have disadvantages. The free
radical polymerization processes require extremely high pressures,
they are limited on the industrial scale to ethylene and ethylene
copolymers, and the required apparatuses are very expensive to
procure and maintain. The other possibility consists in first
polymerizing ethylene in any desired process and then preparing a
secondary dispersion, as described in U.S. Pat. No. 5,574,091. This
method is a multistage process and therefore very complicated.
[0043] It is therefore desirable to polymerize olefins, for example
ethylene or propylene, under the conditions of emulsion
polymerization, and to prepare the required dispersion in one step
from the corresponding olefin. Moreover, emulsion polymerization
processes very generally have the advantage that they give polymers
having high molar masses, the removal of heat being readily
controlled as a result of the process. Finally, reactions in
aqueous systems very generally are of interest because water is a
cheap and environmentally friendly reaction medium.
[0044] Processes presented to date for the emulsion polymerization
of olefins, such as ethylene or propylene, still require
improvement. The problem lies in general in the catalyst required
for the polymerization of these olefins.
[0045] Owing to the considerable commercial importance of
polyolefins, the search for improved polymerization processes
continues to be of great importance.
[0046] A good overview of the prior art on the polymerization of
olefins in an aqueous medium, in particular with the use of
polymerization catalysts prepared in situ, is given by the
non-prior-published Patent Application with Application No.
10234005.6, filed by the Applicant at the German Patent and
Trademark Office. The subject of this Application, which is hereby
incorporated by reference, is the broad use of special quinoid
compounds, usually phosphine or diphosphine compounds and
especially transition metal compounds, for the in situ preparation
of polymerization catalysts and the use thereof for the
polymerization of olefins in an aqueous medium. The in situ
catalysts mentioned in the description as being preferred and used
in the examples were prepared using
2,3,5,6-tetrachloro-para-benzoquinone or
2,3,5,6-tetrabrom-para-benzoquinone and triphenylphosphine as the
ligand compound. However, the use of very poorly water-soluble
organic solvents, for example hexadecane, in the preparation of the
in situ catalysts is not completely satisfactory. Also
unsatisfactory is the fact that the in situ catalysts present as
organic solutions are subjected, before being brought into contact
with the olefin, to a treatment which converts the organic catalyst
solutions into oil-in-water miniemulsions.
[0047] It is an object of the present invention to provide an
improved process which gives polymer dispersions having good
polymer solids contents even without the poorly water-soluble
organic solvents and without the provision of oil-in-water catalyst
miniemulsions.
[0048] We have found that this object is achieved by the process
defined at the outset.
[0049] Examples of suitable olefins for the polymerization are:
ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,
1-octene, 1-decene and 1-eicosene, but also branched olefins, such
as 4-methyl-1-pentene, vinylcyclohexene and vinylcyclohexane, and
styrene, para-methylstyrene and para-vinylpyridine, ethylene and
propylene being preferred. Ethylene is particularly preferred.
[0050] In addition to one of the abovementioned main olefins, at
least one further olefin can also be used as a coolefin for the
polymerization, it being possible to select the at least one
coolefin from the following groups: [0051] ethylene and 1-olefins,
such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,
1-octene, 1-decene and 1-eicosene, but also branched olefins, such
as 4-methyl-1-pentene, vinylcyclohexene and vinylcyclohexane, and
styrene, para-methylstyrene and para-vinylpyridine, propylene,
1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene
being preferred; [0052] internal olefins, such as norbornene,
norbornadiene or cis- or trans-2-butene or cyclopentene; [0053]
polar olefins, such as acrylic acid, C.sub.1-C.sub.8-alkyl
acrylates, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate,
4-hydroxybutyl acrylate, methacrylic acid, C.sub.1-C.sub.8-alkyl
methacrylates, C.sub.1-C.sub.6-alkyl vinyl ethers and vinyl
acetate, and silyloxy compounds, such as 3-(trimethoxysilyl)butyl
methacrylate, 3-(triphenoxysilyl)butyl methacrylate,
vinyltrimethoxysilane, vinyltriethoxysilane or
vinyltriphenoxysilane; acrylic acid, methyl acrylate, ethyl
acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl
acrylate, methyl methacrylate, ethyl methacrylate, n-butyl
methacrylate, ethyl vinyl ether and vinyl acetate are
preferred.
[0054] The ratio of the main olefin to the at least one coolefin
can be freely chosen, the main olefin being used in the mixture to
be polymerized in an amount of .gtoreq.50 mol % and the total
amount of the at least one coolefin being .ltoreq.50 mol %.
Frequently, however, only a main olefin is used for the
polymerization. When at least one coolefin is used, the total
amount of coolefin is often .ltoreq.40, .ltoreq.30, .ltoreq.20 or
.ltoreq.10 mol % and .gtoreq.0.1, .gtoreq.0.5, .gtoreq.1, .gtoreq.5
or .gtoreq.10 mol % and all values in between.
[0055] What is of importance is that frequently olefin mixtures are
used for the novel polymerization, at least one of the olefins used
being ethylene. Ethylene is often the main olefin, and the coolefin
is selected from the group consisting of propylene, 1-butene,
1-hexene and styrene.
[0056] However, it is also possible to use only one olefin for the
polymerization. For this purpose, in particular ethylene,
propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,
1-decene or 1-eicosene is used, but also branched olefins, such as
4-methyl-1-pentene, vinylcyclohexene and vinylcyclohexane, and
styrene, para-methylstyrene and para-vinylpyridine, although
ethylene and propylene are preferred. Ethylene is particularly
preferred.
[0057] In the quinoid compounds of the formulae Ia and Ib, the
radicals are defined as follows:
[0058] R is selected from in each case one or more of the following
radicals: [0059] hydrogen [0060] halogens, i.e. atoms of fluorine,
chlorine, bromine or iodine; fluorine, chlorine and bromine being
preferred [0061] nitrile [0062] C.sub.1-C.sub.12-alkyl groups, such
as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl,
1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl,
n-heptyl, isoheptyl, n-octyl, n-nonyl, n-decyl and n-dodecyl;
preferably C.sub.1-C.sub.6-alkyl, such as methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,
isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl,
n-hexyl, isohexyl or sec-hexyl, particularly preferably
C.sub.1-C.sub.4-alkyl, such as methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl and tert-butyl [0063]
C.sub.1-C.sub.12-alkoxy groups, such as examples mentioned for
C.sub.1-C.sub.12-alkyl groups, in each case also provided with an
oxygen atom at the end of the group (for example methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy) [0064] C.sub.7-C.sub.15-aralkyl
groups having 6 to 10 carbon atoms in the aryl moiety and 1 to 9
carbon atoms in the alkyl moiety, for example
C.sub.7-C.sub.12-phenylalkyl, such as benzyl, phenylethyl,
phenyl-n-propyl, phenylsopropyl or phenyl-n-butyl, particularly
preferably benzyl [0065] C.sub.6-C.sub.14-aryl groups, for example
phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl,
1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and
9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl,
particularly preferably phenyl [0066] amino groups NR.sup.1R.sup.2,
where R.sup.1 and R.sup.2 together or separately are hydrogen,
C.sub.1-C.sub.12-alkyl groups, C.sub.7-C.sub.15-aralkyl radicals or
C.sub.6-C.sub.14-aryl groups (in each case as defined above) and
additionally may also form a saturated or unsaturated 5- to
10-membered ring, the dimethylamino, the diethylamino, the
diisopropylamino and the methylphenylamino group being preferred.
Examples of amino groups having saturated rings are the N-piperidyl
group and the N-pyrrolidinyl group; examples of amino groups having
unsaturated rings are the N-pyrryl group, the N-indolyl group and
the N-carbazolyl group.
[0067] The abovementioned C.sub.1-C.sub.12-alkyl groups,
C.sub.1-C.sub.12-alkoxy groups, C.sub.7-C.sub.15-aralkyl groups,
C.sub.6-C.sub.14-aryl groups and amino groups NR.sup.1R.sup.2 may
each be present in unsubstituted form on the quinoid skeleton of
the formulae Ia and Ib. They can themselves also additionally have
one or more of the following substituents on their own molecular
skeleton: [0068] halogens [0069] C.sub.1-C.sub.12-alkyl groups,
C.sub.1-C.sub.12-alkoxy groups or amino groups having hydrogen
and/or C.sub.1-C.sub.12-alkyl groups, defined as above in each
case; [0070] C.sub.3-C.sub.12-cycloalkyl groups, such as
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,
cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl,
preferably cyclopentyl, cyclohexyl and cycloheptyl; [0071]
C.sub.1-C.sub.12-thioether groups, such as methylmercaptyl,
ethylmercaptyl, n-propylmercaptyl, isopropylmercaptyl,
n-butylmercaptyl, isobutylmercaptyl, tert-butylmercaptyl,
n-pentylmercaptyl, isopentylmercaptyl, neopentylmercaptyl,
n-hexylmercaptyl;
[0072] carboxyl groups, if appropriate also in the form of their
salts, preferably their alkali metal salts, in particular in the
form of their lithium, sodium or potassium salts, and their
ammonium salts;
[0073] sulfo groups, if appropriate also in the form of their
salts, preferably their alkali metal salts, in particular in the
form of their lithium, sodium or potassium salts, and their
ammonium salts.
[0074] It is furthermore possible to use those compounds of the
formulae Ia and Ib which are bridged with one another by one or
more C.sub.1-C.sub.12-alkylene bridges, in particular by one or
more C.sub.2-C.sub.10-alkylene bridges, particularly preferably by
one or more C.sub.3-C.sub.8-alkylene bridges, by one or more
C.sub.2-C.sub.12-alkylated azo bridges, in particular by one or
more C.sub.4-C.sub.10-alkylated azo bridges.
[0075] In addition, identical or different compounds of the
formulae Ia and Ib may also be bridged by bridges of the formula
II
##STR00003##
[0076] where Y is silicon or germanium and R.sup.3 and R.sup.4 are
hydrogen and/or a C.sub.1-C.sub.12-alkyl group. Silicon-based
bridges are preferably used for this purpose.
[0077] Selected quinoid compounds of the formula Ia, which are very
particularly suitable, are shown below as formulae Ia1 to Ia19:
##STR00004## ##STR00005## ##STR00006##
[0078] Particularly suitable quinoid compounds of the formula Ib
are shown below as formulae Ib1 and Ib2:
##STR00007##
[0079] Particularly suitable quinoid compounds which consist of a
plurality of compounds of the formula Ia which are bridged with one
another are shown below as formulae Ia1 and IaII.
##STR00008##
[0080] The synthesis of the quinoid compounds of the formulae Ia
and Ib is known per se. Synthesis methods for such compounds are to
be found, inter alia, in DE-A 2923206, EP-A 046331, EP-A 046328 or
EP-A 052929.
[0081] The compounds Ia and Ib can be used in mixtures in ratios of
from 0:100 to 100:0. Preferred embodiments are 0:100, 10:90, 50:50,
90:10 and 100:0 mol % and all values in between.
[0082] The quinoid compounds of the formulae Ia and Ib and the
metal compound of the formula M(L.sup.2).sub.2,
M(L.sup.2).sub.2(L.sup.1).sub.z, or M(L.sup.1), 2 are combined with
a phosphine compound III of the formula (R').sub.aPH.sub.3-a, where
R' is a C.sub.1-C.sub.12-alkyl group, C.sub.3-C.sub.12-cycloalkyl
group, C.sub.7-C.sub.15-aralkyl group or C.sub.6-C.sub.14-aryl
group which is substituted by at least one polar radical P, the
polar radical P being selected from the group consisting of [0083]
hydroxyl (--OH), carboxyl (--CO.sub.2H), sulfo (--SO.sub.3H),
hydroxysulfonyloxy (--O--SO.sub.3H) or phosphono
(--PO.sub.3H.sub.2) groups and the possible alkali metal, alkaline
earth metal and/or ammonium salts thereof, [0084] alkanolammonium,
pyridinium, imidazolinium, oxazolinium, morpholinium, thiazolinium,
quinolinium, isoquinolinium, tropylium, sulfonium, guanidinium and
phosphonium groups and amino groups of the formula IV [0085]
N.sup..sym.R.sup.7R.sup.8R.sup.9 IV, where [0086] R.sup.7, R.sup.8
and R.sup.9, independently of one another, are hydrogen or a
C.sub.1-C.sub.12-alkyl group,
[0087] or [0088] a group of the formula V, VI or VII [0089]
-(EO).sub.k--(PO).sub.l--R.sup.10 V, [0090]
-(PO).sub.l-(EO).sub.k--R.sup.10 VI, [0091]
-(EO.sub.k/PO.sub.l)--R.sup.10 VII, where [0092] EO is a
--CH.sub.2--CH.sub.2--O-- group, [0093] PO is a
--CH.sub.2--CH(CH.sub.3)--O-- or a --CH(CH.sub.3)--CH.sub.2--O--
group, [0094] k and l are numerical values from 0 to 50, often from
0 to 30 and often from 0 to 15 but k and l are not simultaneously
0, [0095] R.sup.10 is hydrogen, a C.sub.1-C.sub.12-alkyl group or a
sulfo group or the corresponding alkali metal, alkaline earth metal
and/or ammonium salt thereof, and
[0096] a is 1, 2 or 3.
[0097] It is of course also possible for the radical or radicals R'
to be substituted by 2, 3 or even more polar radicals P.
[0098] The quinoid compounds of the formulae Ia and Ib and the
metal compound of the formula M(L.sup.2).sub.2,
M(L.sup.2).sub.2(L.sup.1).sub.z, or M(L.sup.1), 2 can also be
combined with a diphosphine compound VIII of the formula
(R').sub.bPH.sub.2-b-G-PR.sub.2'', where R'' is hydrogen or has the
same meaning as R', G is a C.sub.1-C.sub.12-alkylene group,
C.sub.3-C.sub.12-cycloalkylene group, C.sub.7-C.sub.15-aralkylene
group or C.sub.6-C.sub.14-arylene group, and b is 1 or 2. The
alkylene, cycloalkylene, aralkylene or arylene groups are divalent
functional groups which are derived from the corresponding
abovementioned alkyl, cycloalkyl, aralkyl or aryl groups.
[0099] Of course, mixtures of the phosphine compounds III and VIII
can also be combined with the compounds of the formulae Ia and Ib
and the metal compound of the formula M(L.sup.2).sub.2,
M(L.sup.2).sub.2(L.sup.1).sub.z1, or M(L.sup.1).sub.z2.
[0100] The corresponding anions of the abovementioned polar
radicals IV are normucleophilic anions, for example perchlorate,
sulfate, phosphate, nitrate and carboxylates, such as acetate,
trifluoroacetate, trichloroacetate, propionate, oxalate, citrate or
benzoate, and conjugated anions and organosulfonic acids, for
example methylsulfonate, trifluoromethylsulfonate and
para-toluenesulfonate, and furthermore tetrafluoroborate,
tetraphenylborate, tetrakis(pentafluorophenyl)borate,
tetrakis[bis(3,5-trifluoromethyl)-phenyl]borate,
hexafluorophosphate, hexafluoroarsenate or
hexafluoroantimonate.
[0101] Furthermore, in
[0102] formulae V and VI: (EO).sub.k is intended to be a block of k
--CH.sub.2--CH.sub.2--O-- groups and [0103] (PO).sub.k is intended
to be a block of k-CH.sub.2--CH(CH.sub.3)--O-- or
--CH(CH.sub.3)--CH.sub.2--O-- groups, and
[0104] formula VIII: (EO.sub.k/PO.sub.l) is intended to be a
mixture of k --CH.sub.2--CH.sub.2--O-- groups and l
--CH.sub.2--CH(CH.sub.3)--O-- or --CH(CH.sub.3)--CH.sub.2--O--
groups in random distribution.
[0105] The molar ratio of compound Ia and Ib on the one hand and
phosphine compound III or VIII on the other hand is from 1:1000 to
1000:1, frequently from 1:10 to 10:1, often from 1:2 to 2:1.
[0106] Phosphine compounds III and VIII can be prepared by
conventional syntheses of organic chemistry [in this context, cf.
for example Aqueous-Phase Organometallic Chemistry, B. Cornils, W.
A. Herrmann (Editors), Wiley-VCH, Weinheim, 1998; F. Joo et al.,
Inorg. Synth. 32 (1998), 1 to 43; W. A. Herrmann and C. W.
Kohlpainter, Angew. Chem. 105 (1993), 1588 et seq.; H. Schindbauer,
Monatsh. Ch. 96 (1965), 2051 et seq.; O. Herd et al., Angew. Chem.
105 (1993), 1097 et seq. or DE-A 4141299] and some of them are also
commercially available.
[0107] Examples of phosphine compounds III are in particular [0108]
4-(diphenylphosphino)benzenesulfonic acid, [0109]
3-(diphenylphosphino)benzenesulfonic acid, [0110]
tris(4-sulfophenyl)phosphane, [0111] tris(3-sulfophenyl)phosphane
[0112] and the corresponding alkali metal or ammonium salts
thereof, for example the lithium, sodium, potassium or ammonium
salts thereof, or [0113]
2-(2-{2-[4-(diphenylphosphino)phenoxy]ethoxy}ethoxy)ethanol. [0114]
Examples of phosphine compounds VII are in particular [0115]
1,3-bis(di-4-hydroxyphenyl)phosphinopropane, [0116]
1,3-bis(di-4-hydroxybutyl)phosphinopropane, [0117]
1,3-bis(di-4-methylol-5-hydroxypentyl)phosphinopropane, [0118]
1,3-bis(di-5-hydroxypentyl)phosphinopropane, [0119]
1,3-bis(di-6-hydroxyhexyl)phosphinopropane, [0120]
1,3-bis(di(3-hydroxycyclopentyl)propyl)phosphinopropane, [0121]
1,3-bis(di-8-hydroxyoctyl)phosphinopropane, [0122]
1,3-bis(di(3-hydroxycyclohexyl)propyl)phosphinopropane, [0123]
1,3-bis(di-4-sulfophenyl)phosphinopropane, [0124]
1,3-bis(di-4-sulfobutyl)phosphinopropane, [0125]
1,3-bis(di-4-methylol-5-sulfopentyl)phosphinopropane, [0126]
1,3-bis(di-5-sulfopentyl)phosphinopropane, [0127]
1,3-bis(di-6-sulfohexyl)phosphinopropane, [0128]
1,3-bis(di(3-sulfocyclopentyl)propyl)phosphinopropane, [0129]
1,3-bis(di-8-sulfooctyl)phosphinopropane, [0130]
1,3-bis(di(3-sulfocyclohexyl)propyl)phosphinopropane, [0131]
1,3-bis(di-4-carboxyphenyl)phosphinopropane, [0132]
1,3-bis(di-4-carboxybutyl)phosphinopropane, [0133]
1,3-bis(di-4-methylol-5-carboxypentyl)phosphinopropane, [0134]
1,3-bis(di-5-carboxypentyl)phosphinopropane, [0135]
1,3-bis(di-6-carboxyhexyl)phosphinopropane, [0136]
1,3-bis(di(3-carboxycyclopentyl)propyl)phosphinopropane, [0137]
1,3-bis(di-8-carboxyoctyl)phosphinopropane or [0138]
1,3-bis(di(3-carboxycyclohexyl)propyl)phosphinopropane.
[0139] The quinoid compounds of the formula Ia or Ib are combined
not only with one of the phosphine compounds III or VIII but also
with one or more metal compounds of the formula M(L.sup.2).sub.2,
M(L.sup.2).sub.2(L.sup.1).sub.z1, or M(L.sup.1).sub.z2. The
variables are defined as follows: [0140] L.sup.1 is selected from
phosphanes of the formula (R.sup.5).sub.xPH.sub.3-x or amines of
the formula (R.sup.5).sub.xNH.sub.3-x, where x is an integer from 0
to 3. However, ethers (R.sup.5).sub.2O, such as diethyl ether or
tetrahydrofuran, water, alcohols (R.sup.5)OH, such as methanol or
ethanol, pyridine, pyridine derivatives of the formula
C.sub.5H.sub.5--X(R.sup.5).sub.xN, for example 2-picoline,
3-picoline, 4-picoline, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine,
2,6-lutidine or 3,5-lutidine, carbon monoxide,
C.sub.1-C.sub.12-alkylnitriles or C.sub.6-C.sub.14-arylnitriles,
such as acetonitrile, propionitrile, butyronitrile or benzonitrile,
are also suitable. Furthermore, mono- or polyethylenically
unsaturated double bond systems also serve as the ligand, such as
ethene, propene, cis-2-butene, trans-2-butene, cyclohexene or
norbornene, but also the corresponding radicals thereof.
1,5-Cyclooctadiene (COD), 1,6-cyclodecadiene and
1,5,9-all-trans-cyclododecatriene are frequently used. [0141]
R.sup.5 is selected from hydrogen, C.sub.1-C.sub.12-alkyl groups,
which in turn may be substituted by O(C.sub.1-C.sub.6-alkyl) or
N(C.sub.1-C.sub.6-alkyl).sub.2 groups, and
C.sub.3-C.sub.12-cycloalkyl groups, C.sub.7-C.sub.15-alkyl radicals
and C.sub.6-C.sub.14-aryl groups, where specific examples of these
groups are to be found under the definition of the radical R.
[0142] L.sup.2 is selected from [0143] halide ions, such as
fluoride, chloride, bromide or iodide; chloride and bromide being
preferred, [0144] amide anions
(R.sup.6).sub.yNH.sup..crclbar..sub.2-y, where y is an integer 0, 1
or 2 and R.sup.6 is C.sub.1-C.sub.12-alkyl, [0145]
C.sub.1-C.sub.6-alkyl anions, such as methyl, ethyl, n-propyl,
isopropyl, n-butyl, tert-butyl or n-hexyl anions, [0146] allyl
anions or methallyl anions, [0147] benzyl anions or [0148] aryl
anions, such as the phenyl anion. [0149] M is a transition metal of
groups 7 to 10 of the Periodic Table of the Elements; manganese,
iron, cobalt, nickel and palladium are preferred and nickel is
particularly preferred. [0150] z1 is an integer 1, 2, 3 or 4.
[0151] z2 is an integer 1, 2, 3, 4, 5 or 6, often 4 or 6.
[0152] In a particular embodiment, L.sup.1 and L.sup.2 are linked
to one another by one or more covalent bonds.
[0153] Frequently used metal compounds are olefin complexes of
nickel. A preferred metal compound is Ni(COD).sub.2.
[0154] The conditions for the reaction of the compounds of the
formulae Ia and Ib with the metal compound and at least one of the
phosphine compounds III or VII are not critical per se. Usually,
they are reacted at from 0 to 100.degree. C. in a solvent which may
be selected from aliphatic or aromatic hydrocarbons, for example
n-heptane, toluene, ethylbenzene, ortho-xylene, meta-xylene or
para-xylene. Chlorobenzene is also suitable as a solvent, and
furthermore ketones, for example acetone, acyclic or cyclic ethers,
for example diethyl ether, diisopropyl ether, 1,4-dioxan or
tetrahydrofuran. However, water or water-soluble alcohols, for
example methanol, ethanol, n-propanol, isopropanol or n-butanol,
can also be used as a solvent in the in situ catalyst preparation.
Water, water-soluble alcohols or ketones, for example isopropanol
or acetone, are preferably used.
[0155] Preferably, however, the quinoid compound Ia or Ib is first
mixed with the phosphine compound III or VIII and then reacted with
the metal compound to give the in situ catalyst.
[0156] Ratios of from 1:1000 to 1000:1 have proven useful as the
molar ratio of metal compound to phosphine compound III, preferably
from 1:10 to 10:1 and particularly preferably from 1:2 to 2:1. If a
phosphine compound VIII is used, the corresponding molar ratio is
from 1:500 to 500:1, preferably from 1:5 to 5:1 and particularly
preferably 1:1.
[0157] The molar ratio of metal compound to compound Ia or Ib is
likewise from 1:1000 to 1000:1, preferably from 1:10 to 10:1, in
particular from 1:2 to 2:1.
[0158] It is possible to react the metal compound with the chosen
organic quinoid compounds and the phosphine compound outside the
polymerization reactor and then to introduce the reaction solution
into the polymerization reactor.
[0159] The reaction of metal compound, phosphine compound and
quinoid compound can also be effected inside the polymerization
reactor, and it may be advantageous also to add other substances,
for example emulsifiers or further solvents, monomers to be
polymerized and other assistants, for example activators.
[0160] The choice of the reaction conditions depends in each case
on the substances used. Particularly in the case of water-sensitive
precursors, it has proven advantageous first to react the
precursors outside the polymerization reactor and then to meter the
reaction product into the polymerization reactor.
[0161] This procedure is also advantageous when the precursors do
not dissolve completely in the solvent used, but the reaction
product does.
[0162] Isolation and purification of the complexes formed in situ
(reaction products of metal compound, phosphine compound and
quinoid compound) are dispensed with.
[0163] The complexes produced in situ are very useful in the
polymerization or copolymerization of olefins in water or in a
solvent mixture which contains at least 50% by weight of water. The
polymerization is carried out in the presence of an emulsifier and
optionally in the presence of an activator.
[0164] It is frequently advisable to use an activator in order to
increase the activity of the in situ complex. In the context of
this document, an activator is understood as meaning all those
compounds which are capable of increasing the activity of the in
situ complex.
[0165] The polymerization of the 1-olefins in the novel process can
be carried out in a manner known per se.
[0166] The sequence of addition of the reagent in the
polymerization is not critical. Thus, gaseous monomer can first be
brought into contact with the solvent under pressure or liquid
monomer can be metered in, and the mixture of quinoid compound,
phosphine compound and metal compound is then added. However, the
mixture of quinoid compound, phosphine compound and metal compound
can also first be diluted with further solvent and then monomer
added.
[0167] At the same time, the activator, if it is necessary, is
added either direct or in a solution in a second portion of the
same solvent or in acetone.
[0168] The actual polymerization usually takes place at a minimum
pressure of 1 bar, the polymerization rate being too low below this
pressure. The minimum pressure is preferably 2, particularly
preferably 10, bar (in each case gage pressure).
[0169] The maximum pressure is, for example, 4000 bar; at higher
pressures the requirements with regard to the material of the
polymerization reactor are very high, and the process becomes
uneconomical. .ltoreq.100 bar are preferred and .ltoreq.50 bar are
particularly preferred.
[0170] The polymerization temperature can be varied within a wide
range. The minimum temperature is, for example, .gtoreq.10.degree.
C., since the polymerization rate declines at low temperatures. A
minimum temperature of .gtoreq.40.degree. C. or .gtoreq.65.degree.
C. is preferred. An example of an expedient maximum temperature is
350.degree. C.; .ltoreq.150.degree. C. or .ltoreq.100.degree. C.
are preferred.
[0171] Suitable organic solvents in the aqueous polymerization
medium are aromatic solvents, such as benzene, toluene,
ethylbenzene, ortho-xylene, meta-xylene and para-xylene and
mixtures thereof. Cyclic ethers, such as tetrahydrofuran and
dioxane, or acyclic ethers, such as diethyl ether, di-n-butyl
ether, diisopropyl ether or 1,2-dimethoxyethane, are furthermore
suitable. Ketones, such as acetone, methyl ethyl ketone and
diisobutyl ketone are also suitable, as are amides, such as
dimethylformamide or dimethylacetamide, water-soluble alcohols, for
example methanol, ethanol, n-propanol, isopropanol or n-butanol,
and mixtures of these solvents.
[0172] Acetone or the water-soluble alcohols methanol, ethanol,
n-propanol, isopropanol or n-butanol are preferred as organic
solvents in the aqueous polymerization medium, the mixing ratio of
the organic solvents being arbitrary.
[0173] The amount of the aqueous polymerization medium is likewise
not critical, but it must be ensured that the complex formed in
situ and the activator can dissolve completely, otherwise lower
activities must be expected. The dissolution process can, if
appropriate, be accelerated by ultrasonic treatment.
[0174] The emulsifier which is also to be added can be introduced
into the aqueous polymerization medium either directly or together
with the solution of the catalyst complex formed in situ.
[0175] The amount of the emulsifier is chosen so that the mass
ratio of monomer to emulsifier is greater than 1, preferably
greater than 10, particularly preferably greater than 20. The less
emulsifier which has to be used, the more advantageous.
[0176] As a result of the addition of the emulsifier, both the
polymerization rate and the stability of the aqueous polymer
dispersions formed are increased. The added emulsifier may be
nonionic or ionic.
[0177] Customary nonionic emulsifiers are, for example, ethoxylated
mono-, di- and trialkylphenols (degree of ethoxylation: 3 to 50,
alkyl radical: C.sub.4-C.sub.12) and ethoxylated fatty alcohols
(degree of ethoxylation: 3 to 80; alkyl radical: C.sub.8-C.sub.36).
Examples of these are Lutensol.RTM. grades from BASF AG or
Triton.RTM. grades from Union Carbide.
[0178] Conventional anionic emulsifiers are, for example, alkali
metal and ammonium salts of alkylsulfates (alkyl radical:
C.sub.8-C.sub.12), of sulfuric monoesters of ethoxylated alkanols
(degree of ethoxylation: 4 to 30, alkyl radical: C.sub.12-C.sub.18)
and of ethoxylated alkyphenols (degree of ethoxylation: 3 to 50,
alkyl radical: C.sub.4-C.sub.12), of alkanesulfonic acids (alkyl
radical: C.sub.12-C.sub.18) and of alkylarylsulfonic acids (alkyl
radical: C.sub.9-C.sub.18). It is of course also possible to use
alkyldiphenyl ethers, for example Dowfax.RTM. 2A1 (trademark of Dow
Chemical Company).
[0179] Suitable cationic emulsifiers are as a rule primary,
secondary, tertiary or quaternary ammonium salts, alkanolammonium
salts, pyridinium salts, imidazolinium salts, oxazolinium salts,
morpholinium salts and thiazolinium salts having a
C.sub.6-C.sub.18-alkyl, C.sub.6-C.sub.18-aralkyl or heterocyclic
radical, and salts of amine oxides, quinolinium salts,
isoquinolinium salts, tropylium salts, sulfonium salts and
phosphonium salts. Examples are dodecylammonium acetate or the
corresponding hydrochloride, the chlorides or acetates of the
various 2-(N,N,N-trimethylammonium)ethylparaffin acid esters,
N-cetylpyridinium chloride, N-laurylpyridinium sulfate and
N-cetyl-N,N,N-trimethylammonium bromide,
N-dodecyl-N,N,N-trimethylammonium bromide,
N,N-distearyl-N,N-dimethylammonium chloride and the Gemini
surfactant N,N'-(lauryldimethyl)ethylenediamine dibromide. Numerous
further examples are to be found in H. Stache, Tensid-Taschenbuch,
Carl-HanserVerlag, Munich, Vienna, 1981, and in McCutcheon's,
Emulsifiers & Detergents, MC Publishing Company, Glen Rock,
1989.
[0180] Nonionic and anionic emulsifiers, in particular anionic
emulsifiers, are preferably used for the novel process.
[0181] Polymerization reactors which have proven suitable are
stirred kettles and autoclaves as well as tubular reactors, it
being possible for the tubular reactors to be in the form of a loop
reactor.
[0182] The olefin or olefins to be polymerized is or are mixed in
the aqueous polymerization medium. The polymerization medium used
may be water or a mixture of water with the abovementioned
solvents.
[0183] However, it must be ensured that the amount of water is at
least 50, preferably at least 90, particularly preferably at least
95, % by weight, based in each case on the total polymerization
medium, formed from organic solvent, demineralized water, quinoid
compounds, phosphine and metal compounds, emulsifiers and, if
appropriate, further assistants.
[0184] The solutions of complexes produced in situ, of the
emulsifier and, if appropriate, the activator are combined with the
mixture of monomer and aqueous polymerization medium. The sequence
of addition of the various components is not critical per se.
[0185] However, the components must be combined sufficiently
rapidly to avoid crystallization of sparingly soluble complex
compounds which may occur as intermediates. The molar ratio of
metal compound of the formula M(L.sup.2).sub.2,
M(L.sup.2).sub.2(L.sup.1).sub.z1 or M(L.sup.1).sub.z2 to the olefin
used is 1: .gtoreq.100, 1: .gtoreq.1000, 1: .gtoreq.10 000 or 1:
.gtoreq.100 000 and all values in between. Depending on the
reactivity of the complex formed in situ, the olefin/metal compound
ratio may have even higher values.
[0186] Suitable polymerization processes are in principle
continuous and batchwise processes. Semibatch processes in which
olefin or olefin mixture is further metered in the course of the
polymerization after all components have been mixed are
preferred.
[0187] Aqueous polymer dispersions are initially obtained by the
novel process. Often, these aqueous polymer dispersions have solids
contents of .gtoreq.10, .gtoreq.20 or even .gtoreq.30% by
weight.
[0188] The mean particle diameters of the polymer particles in the
novel dispersions are from 1 to 1000 nm, preferably from 10 to 500
nm, particularly preferably from 10 to 200 nm. The distribution of
the particle diameters can, but need not, be very uniform. For some
applications, in particular for those with high solids contents
(>55% by weight), broad or bimodal distributions are even
preferred. The particle diameters can be determined, for example,
by light scattering methods. An overview is to be found in D.
Distler (Editor), Wassrige Polymerdispersionen, Wiley-VCH Verlag,
1st Edition, 1999, Chapter 4.
[0189] The polymers obtained by the novel process have technically
interesting properties. In the case of polyethylene, they may have
a high crystallinity, which can be detected, for example, by the
number of branches. Frequently, less than 40 branches, preferably
less than 20 branches, particularly preferably less than 10
branches, are present per 1000 carbon atoms of the polymer,
determined by .sup.1H-NMR and .sup.13C-NMR spectroscopy.
[0190] The molecular weight distributions of the polyolefins
obtainable by the novel process, i.e. the Q values (Mw/Mn) are from
1.0 to 50, preferably from 1.5 to 10. The molar masses of the
polyolefins obtained are from 500 to 1 000 000, often from 1000 to
50 000 or from 1000 to 10 000 (number average).
[0191] Also of importance is the fact that the polymer particles
obtained may have different particle morphologies. In particular,
for example, spherical (x axis=y axis=z axis), linear (y axis x
axis and z axis; x axis z axis), acicular (y axis and z axis<x
axis; y 25 axis z axis) and, in the case of polyethylene, also
lamellar polymer particles are obtainable.
[0192] In addition to the advantageous price owing to the cheap
olefinic starting materials and the simple process, another
advantage of the novel dispersions is that they are more stable to
weathering than dispersions of polybutadiene or butadiene
copolymers.
[0193] Compared with dispersions of polymers with acrylates or
methacrylates as the main monomer, the lower tendency to hydrolyse
should be mentioned as being advantageous. Another advantage is
that most olefins are readily volatile, and unpolymerized residual
amounts of olefins can be readily removed. Finally, the fact that,
during the polymerization, it is not necessary to add a molar mass
regulator, for example tert-dodecyl mercaptan, which on the one
hand may be difficult to separate off and on the other hand have an
unpleasant odor, is advantageous. Furthermore, it is advantageous
that the aqueous dispersions obtained from the novel process have a
relatively high solids contents.
[0194] Also of importance is that, in contrast to all known
emulsion polymerization processes, the novel process is
particularly suitable for the preparation of aqueous polymer
dispersions of very small polyethylene particles. The small
particle sizes result in complete or virtually complete
transparency of the aqueous polymer dispersions.
[0195] The polymer particles can be obtained from the initially
obtained aqueous dispersions by removing the water and any organic
solvent or solvents. Numerous conventional methods are suitable for
removing the water and any organic solvent or solvents. For example
freeze drying, spray drying or evaporation. The polymer particles
thus obtained have a good morphology and a high bulk density.
[0196] The dispersions prepared according to the invention can be
advantageously used in numerous applications, for example paper
applications, such as paper coating or surface sizing, and
furthermore in paints and finishes, construction chemicals,
adhesive raw materials, molded foams, textile and leather
applications, carpet backing coatings, mattresses or pharmaceutical
applications.
[0197] Paper coating is understood as meaning the coating of the
paper surface with aqueous pigmented dispersions. Owing to their
favorable price, the dispersions prepared according to the
invention are advantageous. Surface sizing is understood as meaning
the pigment-free application of substances imparting water
repellency. In particular, the polymer dispersions obtainable to
date under economical conditions only with difficulty are
particularly hydrophobic substances and therefore advantageous.
Another advantage is that, during the novel preparation of the
dispersions for paper coating or surface sizing, it is not
necessary to add any molar mass regulators, for example
tert-dodecyl mercaptan, which on the one hand may be difficult to
separate off and on the other hand have an unpleasant odor.
[0198] The dispersions prepared according to the invention are
particularly suitable in paints and coatings because they have a
very advantageous price. Particularly advantageous are aqueous
polyethylene dispersions because they furthermore have particular
UV stability. Aqueous polyethylene dispersions are furthermore
particularly suitable because they are resistant to basic chemicals
which are customary in construction chemistry.
[0199] The dispersions prepared according to the invention have
economic advantages in adhesives, in particular in adhesives for
self-adhesive labels or films and plasters, but also in
construction adhesives or industrial adhesives. Particularly in
construction adhesives, they are especially advantageous because
they are resistant to basic chemicals which are customary in
construction chemistry.
[0200] In molded foams which can be produced by processes known per
se, such as the Dunlop process or the Talalay process, from the
dispersions prepared according to the invention, the advantageous
price of the novel dispersions is once again advantageous. Gelling
agents, soaps, thickeners and vulcanization pastes serve as further
components. Molded foams are processed, for example, to give
mattresses.
[0201] Textile and leather applications serve for stabilizing and
finishing textile or leather. Among the effects, the impregnation
and the further finishing of the textiles may be mentioned by way
of example. In addition to the favorable price, another advantage
of the dispersions prepared according to the invention as component
in textile and leather applications is the freedom from odor, since
the residual amounts of olefin in the aqueous dispersions can be
readily removed.
[0202] Carpet backing coatings serve for adhesively bonding carpet
fibers to the backing and furthermore perform the function of
giving the carpet the necessary stiffness and of uniformly
distributing additives, for example flameproofing agents or
antistatic agents. In addition to the favorable price, another
advantage of the dispersions prepared according to the invention is
the insensitivity to the conventional additives. In particular,
polyethylene dispersions have proven to be particularly chemically
inert. Finally, the fact that, during the novel preparation of the
dispersions for carpet backing coatings, it is not necessary to add
any molar mass regulators, for example tert-dodecyl mercaptan which
have the abovementioned disadvantages, is advantageous.
[0203] Pharmaceutical formulations are understood as meaning
dispersions as carriers of medicaments. Dispersions as carriers of
medicaments are known per se. Advantages of the dispersions
prepared according to the invention as carriers of medicaments is
the favorable price and the resistance to body influences, such as
gastric juice or enzymes.
WORKING EXAMPLES
[0204] General: Unless stated otherwise, the syntheses were carried
out by the Schlenk method in the absence of air and moisture under
an argon atmosphere.
[0205] The molar masses of the polymers obtained were determined by
means of GPC. On the basis of DIN 55672, the following conditions
were chosen: solvent: 1,2,4-trichlorobenzene, flow rate: 1 ml/min;
temperature: 140.degree. C. Measurement was effected using a Waters
150 C apparatus which had been calibrated using polyethylene
standards.
[0206] The solids content was determined by precipitating the
polyethylene with methanol.
Example
[0207] 24.5 mg (100 .mu.mol) of
2,3,5,6-tetrachloro-para-benzoquinone (Ia1) and 38 mg (100 .mu.mol)
of the potassium salt of 4-(diphenylphosphino)benzenesulfonic acid
were dissolved in 10 ml of anhydrous and degassed isopropanol at
from 20 to 25.degree. C. (room temperature) in a Schlenk flask with
stirring and under an argon inert gas atmosphere, the solution
acquiring an orange color. This solution was transferred under an
argon atmosphere into another Schlenk flask, which contained 30.3
mg (110 .mu.mol) of nickel (1,5-cyclooctadiene).sub.2
[Ni(COD).sub.2], and was stirred for 20 minutes.
[0208] In the meantime, a solution of 1 g of sodium dodecylsulfate
(SDS) in 90 ml of degassed and demineralized water was prepared.
This solution was introduced at room temperature under an argon
atmosphere into a pressure-resistant 300 ml reactor. The
isopropanolic solution of catalyst prepared in situ was likewise
added to the reactor with stirring (1000 revolutions per minute).
Ethylene was then forced into the reactor to a pressure of 40 bar
(gage pressure). Thereafter, the liquid reactor content was heated
to 70.degree. C. with stirring and left at this temperature for 2
hours. Thereafter, the reactor content was cooled to room
temperature and let down to atmospheric pressure. The polymer
dispersion obtained exhibited only slight turbidity.
[0209] 60 g of methanol were added to 40 g of the aqueous polymer
dispersion obtained, with stirring, 5.32 g of polyethylene
(corresponding to a polymer solids content of 13.3% by weight)
being precipitated. The polymer had a number average molecular
weight of about 6000 g/mol and a weight average molecular weight of
about 32 400. The melting point of the polyethylene was 129.degree.
C.
Comparative Example
[0210] The comparative example was effected analogously to the
example, except that, instead of the potassium salt of
4-(diphenylphosphino)benzenesulfonic acid, 26.3 mg of unsubstituted
triphenylphosphine were used.
[0211] After the end of the reaction and precipitation with
methanol, 0.3 g of polyethylene, corresponding to a polymer solids
content of 0.7% by weight, was obtained.
* * * * *