Method of producing modified vinyl ether polymers

Details Method of producing modified vinyl ether polymers Method of producing modified vinyl ether polymers

2000-03-21

2003-01-28

Wilson, D. R. (Department: 1713)

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

Synthetic resins

Mixing of two or more solid polymers; mixing of solid...

C525S364000, C525S370000, C525S371000, C525S384000, C525S328900

Reexamination Certificate

active

06512058

ABSTRACT:

A method of producing modified vinyl ether polymers
The present invention relates to a method of producing modified vinyl ether polymers.
Polyvinylalkyl ethers are interesting polymers which can be used in diverse ways, e.g. as additives in electro-deposition paints, as flow enhancers in powder coatings, as adhesives for paper, as thickeners for aqueous systems, as plasticisers for resins and as care media for floors.
These homopolymers are preferably produced by cationic polymerisation, since radical-initiated polymerisation results in poor yields.
C
2
-C
4
alkylvinyl ethers are preferably used for homopolymerisation, since these monomers are commercially available on a large scale.
Modifications of these homopolymers would be more suitable for certain applications. For example, polybutylvinyl ethers are not compatible with water and can only be converted into an emulsion via external emulsifiers or by complicated procedures such as those described in EP-A-0 379 166. The production of modified vinyl ether polymers is only possible with restrictions, since corresponding monomers are only obtainable to a limited extent. The transetherification of monomeric vinyl ethers with replacement of the alkyl group in order to produce new monomeric vinyl ethers is in fact described in the literature (McKeon, J. E.; Filton, P.; Griswald, A. A.; Tetrahedron 28, 227 (1972) and 28, 233 (1972); M. A. Smith, K. B. Wagener, Polymer Preprints 28, 264 (1987); J. P. 59055845A2840331 (1984), EP 92 117 174). Despite this, the vinyl ethers which are described in these literature references are not commercially available on a large scale.
It is the object of the present invention to identify a method which provides ease of access to modified polyvinylalkyl ethers. The expression “modified” should be understood here, for example, to be the introduction of hydrophilic groups which improve the compatibility with water. It is also possible by the method according to the invention, however, to introduce other functional or reactive groups into the vinyl ether polymers used as starting materials, in order to change the properties thereof. In this manner, modified vinyl ether polymers can be produced which are not obtainable by the polymerisation of corresponding monomers.
Surprisingly, this object has been achieved by subjecting unmodified polyalkylvinyl ethers to a transetherification reaction in which the alkyl radicals of the polymer are partially replaced by other groups. Examples of transetherification components which can be used in the method according to the invention include
saturated aliphatic alcohols such as tridecyl alcohol, lauryl alcohol, stearyl alcohol and behenyl alcohol,
unsaturated aliphatic alcohols such as oleyl alcohol, 1-undecanol and 1-hexenol, and araliphatic alcohols such as benzyl alcohol and phenylethanol.
The present invention therefore relates to a method of the type described before, wherein vinyl ether polymers comprising recurring units of general formula (I)
where R represents a C
2
-C
4
alkyl group and x denotes an integer from 10 to 1000, are partially transetherified with compounds of general formula Y—OH, wherein Y represents aliphatic and/or cycloaliphatic hydrocarbon groups comprising 5 to 30 carbon atoms, the hydrogen atoms of which can be replaced at least in part by halogen atoms and/or aryl radicals, and/or represents aliphatic, cycloaliphatic and/or aromatic groups with a molecular weight of up to 6000 which contain at least one ether group —O— or an ester group —COO— within the molecule, in the presence of compounds of the platinum metals with the release of the corresponding C
2
-C
4
alcohols, wherein statistically at least one R radical is replaced by a Y radical per molecule of vinyl ether polymer.
0.5 to 25 mol % of the R radicals are preferably transetherified. 1 to 15 mol % of the R radicals are more preferably transetherified, and 2 to 10 mol % of the R radicals are most preferably transetherified.
Even though the transetherification of monomeric vinyl ethers has been described, i.e. the transfer of the vinyl group of a vinyl ether or divinyl ether to the OH group of another alcohol, it has not proved possible to find any reference to the transetherification of polymeric vinyl ethers. The success of this transetherification reaction of polymeric vinyl ethers is surprising, particularly since the transetherification of unsaturated vinyl ethers, which is described in EP-A-0 538 681 for example, is often conducted in saturated ethers such as diethyl ether, ethylene glycol ether, propylene glycol ether or butylene glycol ether, using the same catalysts which are used in the method according to the present invention (EP 0 538 681).
Compounds from the category of the platinum metals are used as catalysts, most preferably compounds of platinum, palladium, rhodium, ruthenium or mixtures thereof. Platinum metal catalysts are most preferably used, such as hexachloroplatinic acid and Speier's catalyst. Chelates of platinum compounds are also suitable, such as those of 2,2-bipyridine and phenanthroline for example.
Cornmercially available polyvinylalkyl ethers with different molecular weights, such as polyvinylethyl ethers (Lutonal® A 25) or polyvinylisobutyl ethers (Lutonal® I 30 or Lutonal® I 60), are used as starting materials, i.e. as vinyl ether polymers comprising recurring units of formula I.
However, C
2
-C
4
polyvinylalkyl ethers with different molecular weights and different compositions of their alkyl radicals, which are produced by cationic polymerisation by known methods, can also be used for the method according to the invention.
Alkali-free aliphatic, cycloaliphatic and/or araliphatic compounds, which each contain 5-30 carbon atoms, can be used as monohydroxy compounds of general formula Y—OH. Mixtures of such compounds can also be used.
Straight chain and branched aliphatic or araliphatic compounds can be used. These can be saturated or unsaturated. Saturated compounds are preferred. Hydrogen atoms can be replaced in part by halogens, preferably by fluorine and/or by chlorine also. If substituted compounds of this type are used, they are preferably aliphatic monoalcohols. Products of this type are commercially available, wherein, as is known to one skilled in the art, the carbon atoms close to the hydroxyl group generally comprise no halogen atoms. Heptadecafluorodecanol or C
6
F
13
CH
2
CH
2
OH are examples of special fluorinated alcohols. The corresponding commercially available products are often not homogeneous, but are mixtures of different fluorinated compounds such as those which are obtained during industrial synthesis.
Monohydroxy compounds which contain at least one —O— and/or ester group can also be used as monohydroxy compounds of formula Y—OH. These are therefore mono- or polyethers, esters or polyesters, or mixed polyether polyesters. Apart from ether groups, the compound Y—OH can also contain amide groups and urea groups, or can contain amide groups or urea groups on their own. Examples of ester-containing compounds or polyesters are those which can be obtained by the addition of a lactone such as propiolactone, valerolactone, caprolactone or substituted derivatives thereof by means of a monohydroxy starting component. The compounds which are used as starting components include monoalcohols, which advantageously comprise 1-30, preferably 4-14 C atoms, such as n-butanol for example, longer-chain saturated and unsaturated alcohols such as propargyl alcohol, oleyl alcohol, hexenol, oxoalcohols, cyclohexanol, phenylethanol, neopentyl alcohol, and also fluorinated alcohols such as those mentioned above. Alcohols of the type described above, and substituted and unsubstituted phenols, can also be converted, by alkoxylation by known methods with ethylene oxide and/or propylene oxide, into polyoxyalkylene monoalkyl, aryl, aralkyl and cycloalkyl ethers, and these monohydroxy polyethers can be used in the manner described above as starting components for subsequent lactone addition. Mixtures of the aforementioned compounds can also be u

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