Graft copolymers, their preparation and their use

Details Graft copolymers, their preparation and their use Graft copolymers, their preparation and their use

2003-07-14

2004-09-14

Seidleck, James J. (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...

C525S105000, C525S193000, C525S263000, C525S273000, C525S333300, C525S333400, C525S227000, C525S359100, C525S359600, C526S292600, C524S458000, C524S567000, C524S577000

Reexamination Certificate

active

06790909

ABSTRACT:

The present invention relates to a process for preparing a functionalized reaction product (RP) by reaction under free-radical conditions and also to the functionalized reaction product itself and to its use as macroinitiator for the preparation of graft copolymers. Furthermore, the present invention relates to a process for preparing graft copolymers by reaction of the reaction product (RP), to graft copolymers which can be prepared by this process and to the use of the graft copolymers which can be prepared according to the present invention.
Graft copolymers are target structures which are steadily increasing in importance in polymer chemistry. Such polymers are suitable for numerous applications, in particular for use in polymer mixtures to match the properties, of these mixtures to a desired property profile. There are various methods for preparing graft copolymers. One of the most efficient ways of preparing defined graft copolymers is the preparation of graft copolymers by grafting from a defined macroinitiator onto which suitable monomers are grafted by cationic polymerization.
A large number of macroinitiators which are suitable for free-radical or ionic polymerization and have been prepared by virtually all possible polymerization techniques is known from the prior art. However, a difficulty is the introduction of, for example, initiator functions suitable for cationic polymerization into the macroinitiator. Examples of such interesting initiator functions are groups containing halogen or sulfonyl chloride. However, the preparation of defined macroinitiators functionalized by the functional groups mentioned by customary free-radical polymerization processes is problematical, since these initiator functions have a strong transfer tendency and are also reactive toward anionic catalysts or transition metal catalysts. Various approaches to solutions to this problem are known from the prior art.
Thus, Bertin et al., Polymer Bull 1996, 37, 337, describe the controlled free-radical polymerization (CRP) of 4-vinylbenzyl chloride. (CMS) using TEMPO and its copolymerization with styrene. However, the use of TEMPO is restricted to styrene derivatives since TEMPO is not suitable for the polymerization or copolymerization of polar monomers such as methyl methacrylate (MMA).
ATRP (atom transfer radical polymerization) is also unsuitable for preparing the desired macroinitiators functionalized by groups containing halogen or sulfonyl chloride, since halogen-containing monomers are themselves initiators for the ATRP.
Furthermore, controlled free-radical polymerization in the presence of diphenylethene (DPE) or its derivatives is known from the prior art.
WO 00/37507 relates to a process for preparing a reaction product (A), which comprises the step (i):
(i) reaction under free-radical conditions of a reaction mixture comprising at least one free-radically reactable monomer (a) in the presence of at least one free-radial initiator and a compound of the formula
 where R
1
to R
4
are each independently of one another, hydrogen, an in each case unsubstituted or substituted alkyl radical cycloalkyl radical or aralkyl radical or an unsubstituted or substituted aromatic hydrocarbon radical, with the proviso that at least two of R
1
to R
4
are unsubstituted or substituted aromatic hydrocarbon radicals, in an aqueous phase,
and also to a process for preparing a polymer using this reaction product. Reaction products which bear groups containing halogen or sulfonyl chloride and are thus suitable as macroinitiators, in particular for cationic polymerization, are not disclosed. DE-A 199 61 063 relates to a process for preparing a reaction product (A), which comprises the step (i):
(i) reaction under free-radical conditions of a reaction mixture comprising at least one free-radically reactable monomer (a) in the presence of at least one -free-radical initiator and a compound of the formula
 where R
1
to R
4
are each, independently, of one another, hydrogen, an unsubstituted or substituted alkyl radical, cycloalkyl radical or aralkyl radical or an unsubstituted or substituted aromatic hydrocarbon radical, with the proviso that at least two of the radicals R
1
to R
4
are unsubstituted or substituted aromatic hydrocarbon radicals, or the radicals R
1
and R
2
or R
3
and R
4
in each case in pairs form a substituted or unsubstituted aromatic hydrocarbon having from 6 to 18 carbon atoms and bearing a functional group which has a multiple bond between a carbon atom and a heteroatom which is conjugated with the C—C double bond in the formula I,
where 10% by weight or less of water is present in the reaction mixture during the reaction.
DE-A 199 61 063 also relates to a process for preparing a polymer using the reaction product (A). This patent application, too, does not disclose any reaction products bearing groups containing halogen or sulfonyl chloride.
It is an object of the present invention to provide a process for preparing reaction products functionalized by groups containing halogen or sulfonyl chloride, with monomers containing halogen or sulfonyl chloride being able to be incorporated into the polymers without the groups containing halogen or sulfonyl chloride being lost in the process, so as to give polymers bearing groups which contain halogen or sulfonyl chloride and are suitable as initiator function. Such polymers have a great potential for numerous applications.
We have found that this object is achieved by a process for preparing a reaction product (RP) functionalized by groups containing halogen or sulfonyl chloride by reaction of the following components under free-radical conditions:
a) at least one free-radically polymerizable monomer as component (A),
b) at least one compound of the formula (I) as component (B)
 where R
1
to R
4
are each, independently of one another, hydrogen, an in each case unsubstituted or substituted alkyl radical, cycloalkyl radical or an aralkyl radical or an unsubstituted or substituted aromatic hydrocarbon radical, with the proviso that at least two of the radicals R
1
to R
4
are unsubstituted or substituted aromatic hydrocarbon radicals or the radicals R
1
and R
2
or R
3
and R
4
in each case in pairs form a substituted or unsubstituted aromatic hydrocarbon having from 6 to 18 carbon atoms and bearing a functional group which has a multiple bond between a carbon atom and a heteroatom which is conjugated with the C—C double bond in the formula (I),
c) at least one free-radical initiator as component (C),
d) at least one free-radically polymerizable monomer containing halogen or sulfonyl chloride groups as component (D).
A further object of the invention is to provide a process for preparing defined graft copolymers.
We have found that this object is achieved by a process for preparing graft copolymers by reaction of a reaction product (RP) as defined in the present patent application with at least one suitable monomer (component (E)). This reaction is preferably a cationic polymerization.
Component A
For the purposes of the process of the present invention, it is possible to use all free-radically reactable monomers as monomers (component A).
For example, free-radically homopolymerizable or copolymerizable compounds which bear a hydrophilic group, e.g. a carboxyl group, can be used as monomers (component A). In this case, the monomers (component A) are hydrophilic, free-radically homopolymerizable or copolymerizable monomers, i.e. monomers whose solubility in water is higher than that of styrene.
Of course, it is also possible to use mixtures of various hydrophilic monomers as monomers (component A) for the purposes of the present invention.
However, in a further embodiment of the present invention, it is also possible to use free-radically polymerizable monomers which have a solubility in water which corresponds to or is lower than that of styrene.
Furthermore, mixtures of at least one hydrophilic monomer and at least one hydrophobic monomer can also be polymerized by the process of the present invention. Specific examp

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