Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2002-06-13
2004-11-09
Acquah, Sam A. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S263000, C525S273000, C525S241000, C525S391000, C526S292500
Reexamination Certificate
active
06815498
ABSTRACT:
The present invention relates to a process for the preparation of a reaction product (A) by reaction, under free radical conditions, of at least one monomer (a), capable of free radical polymerization, in the presence of at least one free radical initiator and a compound of the formula (I) as defined below, this reaction product per se, a process for the preparation of a polymer using this reaction product, and its use as a macroinitiator.
The present invention relates to the technical field of free radical polymerization which has features which are typical of a living polymerization system, the novel process being capable in principle of providing reaction products or polymers which may have a narrow molecular weight distribution (M
w
/M
n
). In addition, both straight-chain and branched homopolymers and copolymers as well as block copolymers can be prepared by an appropriate choice of monomers and, if required, successive addition of different monomers. The present invention relates not only to the polymers per se but also to a reaction product obtained in a first stage.
There has for some years been considerable interest in processes or process concepts which are suitable for the preparation of a multiplicity of polymers and make it possible to provide such polymers having a predetermined structure, molecular weight and molecular weight distribution.
Thus, WO 98/01478 describes a process for the preparation of polymers, in which the monomer to be reacted, which is chosen in particular from vinyl monomers and from acid derivatives having unsaturated groups, for example anhydrides, esters and imides of (meth)acrylic acid, is reacted in the presence of a free radical initiator and of a thiocarbonylthio compound as a chain-transfer agent.
WO 92/13903 describes a process for the preparation of polymers having a low molecular weight by free radical chain polymerization of one or more monomers in the presence of a group-transfer agent as defined therein, which has a C—S double bond. According to this publication, the compounds described there and having a C—S double bond act not only as chain-transfer agents but also as growth regulators, so that, according to this publication, it is only possible to prepare polymers having a low molecular weight in the presence of this compound.
A process for the free radical chain polymerization of unsaturated monomers in an aqueous medium and in the presence of a macromonomer having a terminal —CH
2
—C(X)═CH
2
group, where X is as defined therein, is described in WO 93/22351. According to the examples of this application, various (meth)acrylates or (meth)acrylic acid and, if desired, monomers such as styrene are each reacted there under emulsion or suspension polymerization conditions.
WO 93/22355 relates to a process for the preparation of crosslinkable polymers using a macromonomer as described in WO 93/22351.
WO 96/15157 likewise describes a process for the preparation of polymers having a comparatively narrow molecular weight distribution, in which a vinyl monomer as defined therein is reacted with a macromonomer, which is likewise vinyl-terminated, in the presence of a free radical initiator.
Furthermore, WO 98/37104 relates to the preparation of polymers controlled with respect to the molecular weight, including those based on acrylate, by free radical polymerization of corresponding monomers using a chain-transfer agent defined in more detail therein and having a C—C double bond and radicals which activate this double bond with respect to the free radical addition of monomers.
A free radical chain polymerization or copolymerization with an &ohgr;-unsaturated oligo(methyl methacrylate) using ethyl acrylate, styrene, methyl methacrylate, acrylonitrile and vinyl acetate as copolymers is described in a scientific article in J. Macromol. Sci.-Chem., A 23 (7) (1986), 839-852.
In view of this prior art, it is an object of the present invention to provide a novel process for the preparation of a polymeric reaction product which leads in a simple and controlled manner to homopolymers and copolymers which can be prepared by a free radical method. It is a further object of the present invention to provide a process with the aid of which it is possible to prepare block copolymers which are obtainable only in an unsatisfactory manner, if at all, by other routes. It is furthermore an object of the present invention to permit properties of polymers to be established in a controlled manner and hence to permit a wide range of potential uses of such polymers which are obtainable by simple free radical polymerization.
We have found that this and further objects are achieved by the novel process as described below.
The present invention therefore relates to a process for the preparation of a reaction product (A), which comprises the following stage (i):
(i) Reaction, under free radical conditions, of a reaction mixture comprising
at least one monomer (a) capable of free radical polymerization,
at least one free radical initiator and
a compound of the formula (I)
where R
1
to R
4
, independently of one another, are each hydrogen, an alkyl radical, cycloalkyl radical or aralkyl radical, each of which is unsubstituted or substituted, a substituted or unsubstituted aromatic hydrocarbon radical, with the proviso that at least two of the radicals R
1
to R
4
are an unsubstituted or substituted aromatic hydrocarbon radical, or R
1
and R
2
or R
3
and R
4
, in pairs in each case, are a substituted or unsubstituted aromatic hydrocarbon having 6 to 18 carbon atoms and a functional group which, in conjugation with the C—C double bond in the formula I, has a multiple bond between a carbon atom and a heteroatom,
10% by weight or less of water being present in the reaction mixture during the reaction.
The present invention furthermore relates to a reaction product (A) which can be prepared by means of a process comprising the following stage (i):
(i) Reaction, under free radical conditions, of a reaction mixture comprising at least one monomer (a), capable of free radical reaction, in the presence of at least one free radical initiator and of a compound of the formula (I)
where R
1
and R
4
, independently of one another, are each hydrogen, an alkyl radical, cycloalkyl radical or aralkyl radical each of which is unsubstituted or substituted, an unsubstituted or substituted aromatic hydrocarbon radical, with the proviso that at least two of the radicals R
1
to R
4
are a substituted or unsubstituted aromatic hydrocarbon radical, or R
1
and R
2
or R
3
and R
4
, in pairs in each case, are a substituted or unsubstituted aromatic hydrocarbon having 6 to 18 carbon atoms and a functional group which, in conjugation with the C—C double bond in formula I, has a multiple bond between a carbon atom and a heteroatom,
10% by weight or less of water being present in the reaction mixture during the reaction.
In the above novel process, all monomers capable of free radical reaction may be used as monomer (a).
For example, compounds which are capable of free radical homopolymerization or copolymerization and comprise a hydrophilic group, e.g. a carboxyl group, can be used as monomers (a). In this case, the monomers (a) are hydrophilic monomers capable of free radical homopolymerization or copolymerization, i.e. monomers whose solubility in water is higher than that of styrene.
Of course, mixtures of different hydrophilic monomers can also be used as monomers (a) in the present invention.
In a further embodiment of the present invention, however, it is also possible to use monomers which are capable of free radical polymerization and have a water solubility which corresponds to or is even lower than that of styrene.
In addition, mixtures of at least one hydrophilic monomer and at least one hydrophobic monomer can also be polymerized by the novel process. Specific examples of monomers (a) are:
C
1
- to C
20
-alkyl and hydroxyalkyl esters of monoethylenically unsaturated C
3
- to C
10
-monocarboxylic acids or C
4
- to C
8
-dicarboxylic acids, for example methyl
Braun Frank
Brinkmann-Rengel Susanne
Christie David
Haremza Sylke
Modery Bernd
Acquah Sam A.
Asinovsky Olga
BASF - Aktiengesellschaft
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
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