COPOLYMERES D'ACIDES CARBOXYLIQUES INSATURES ET LEUR UTILISATION

COPOLYMERS OF UNSATURATED CARBOXYLIC ACIDS AND USE THEREOF

Abrégé anglais

ABSTRACT
The present invention relates to co-
polymers based on unsaturated carboxylic acids and
sugars capable of forming enolates, obtainable by
copolymerizing the unsaturated carboxylic acids in
an amount of from 35 to 80%, based on the total
monomers, with an alkaline solution of at least one
of palatinose and leucrose in the presence of free
radical initiators at temperatures of between 60°C
and 110°C, while at least one of the two monomers is
continuously supplied, then cooled and precipitated
by acidification. The copolymers of the present
invention are excellently suitable as sequestrants,
complexants and co-builders in washing and cleaning
agents.

Revendications

The embodiments of the invention in which an exclu-
sive property or privilege is claimed are defined
as follows:
1. Copolymers based on unsaturated carboxylic
acids and sugars capable of forming enolates, obtain-
able by copolymerizing the unsaturated carboxylic
acids in an amount of from 35 to 80%, based on the
total monomers, with an alkaline solution of at least
one of palatinose and leucrose in the presence of
free radical initiators at temperatures of between
60°C and 110°C, while at least one of the two mono-
mers is continuously supplied, then cooled and
precipitated by acidification.
2. Copolymers according to claim 1, obtain-
able by the reaction of the alkaline solution of at
least one of palatinose and leucrose at a pH value of
from 8 to 10 with at least one of acrylic acid and
methacrylic acid in the presence of hydrogen
peroxide.
3. Copolymers according to claim 1 or 2,
wherein the alkaline solution is palatinose.
4. Copolymers according to claim 1 or 2,
wherein the alkaline solution is leucrose.
5. A process for preparing copolymers of
unsaturated carboxylic acids and sugars capable of
forming enolates which comprises copolymerizing the
unsaturated carboxylic acids in an amount of from 35
to 80%, based on the total monomers, with an alkaline
solution of at least one of palatinose and leucrose

in the presence of free radical initiators at
temperatures of between 60°C and 110°C, while at
least one of the two monomers is continuously
supplied, then cooled and precipitated by acidifica-
tion.
6. Use of the copolymers according to claim 1
or 2 as sequestrants, complexants and co-builders in
washing and cleaning agents.

Description

1 323627
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Copolymers of Unsaturated Carboxylic Acids
and Use Thereof
The subject matter of the main application Serial-
No. 565,054 is comprised of copolymers based on un-
saturated carboxylic acids and monosaccharides capable
of forming enolates, which copolymers are obtainable by
that the unsaturated carboxylic acids in an amount of
from 35 to 80~, based on the total monomers, are copoly-
merized with an alkaline solution of the monosaccharides
capable of forming enolates in the presence of free
radical initiators at temperatures of between 60 C and
110 C, while at least one of the two monomers is con-
tinuously supplied to the reaction batch, then cooled
and precipitated by acidification. Furthermore, the
main application relates to the use of said copolymers
as sequestering agent (sequestrant), complexing agent
(complexant) and co-builder in washing and cleaning
agents.
It has now been found that, besides the mono-
saccharides capable of forming enolates, also the
disaccharides palatinose and leucrose are capable of
forming enolates and, thus, can be polymerized with
unsaturated carboxylic acids in the same manner.
., .
Palatinose is a 6-O-~-D-glucopyranosyl-D-
fructose, and leucrose is a 5-O-~-D-glucopyranosyl-D-
fructose. These sugars are formed, for example, by the
reaction of saccharose and fructose in the presence of
glycosyl-transferases. For example, palatinose is
produced by the Sudzucker AG in Frankenthal, and so is
leucrose in larger amounts by Pfeifer & Langen in
Dormagen.
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The saccharose as theoretically capable of form-
ing enolates, apparently, is sterically hindered to such
a degree that any copolymerization with unsaturated
carboxylic acids is not possible.
In the free radical copolymerization, palatinose
as well as leucrose do very violently react with acrylic
acid and yield products which are slightly yellowish in
color and have a comparably good calcium binding
capacity. However, the degree of biodegradability of in
excess of 95% is even more favourable than that of the
copolymers according to the main application.
The preparation of the copolymers of palatinose
and of leucrose is carried out in the same manner as
that of the monosaccharides capable of forming enolates.
It is a particular advantage that also unpurified fract-
ions or fractions contaminated with other saccharides
of palatinose and leucrose may be employed, since the
contaminants will either not or not in an interfering
condition be incorporated in the copolymer. In as much
as glycosyl transferases which are not sufficiently
specific or consist of mixtures of various glycosyl
transferases, are employed in the preparation of the
palatinose or leucrose, there will be obtained mother
liquors in the preparation of the palatinose or
leucrose, in which both palatinose and leucrose are
present. A separation of such mixture is possible only
with extreme difficulties. Nevertheless, such mother
liquors may be readily employed in the preparation of
the copolymers according to the invention.
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The usable unsaturated carboxylic acids again
include, in the first place, the monoethylenically
unsaturated monocarboxylic acids having from 3 to 10
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; methacrylic acid. However, basically other
unsaturated carboxylic acids such as maleic acid,
itaconic acid, etc. may be used as well.
As the radical-forming initiators, there are
particularly used peroxides. Particularly simple is
the use of hydrogen peroxide.
The calcium binding capacity of the
copolymers according to the invention is determined,
for example, by turbidimetric titration using
` calcium acetate. To this end, 1 g of the copolymer
to be examined is dissolved in 100 ml of distilled
water, and then 10 ml of a 2~ sodium carbonate
solution are added thereto. The pH of this solution
is adjusted to 11 and kept constant during the
titration. The titration is carried out by adding a
i 4.4~ calcium acetate solution until a distinct
constant turbidity occurs which is determined by
nephelometry. The addition of the calcium acetate
solution is effected by adding amounts of 1 ml at
intervals of 30 seconds each.
Copolymers according to the present invention
- are obtainable by reaction of alkaline solution of
' palatinose and/or leucrose at pH value of from 8 to
10 with acrylic acid and/or methacrylic acid in the
-i presence of hydrogen peroxide.
Some typical copolymers and the preparations
thereof are described in the following examples.
EXAMPLE 1
`~ One hundred-eighty grams of palatinose are
dissolved in 220 g of water and charged in a
reaction vessel. To this solution there are added
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-` 1 323627
- 4a -
108 g of acrylic acid and 57 g of 30~ H202. The
solution is heated at from 60C to 65C with
stirring. Then the heat supply is stopped. Due to
the exothermal reaction,
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the temperature rises to $0 C, whereupon by cooling the
temperature is kept to remain constant at 80 C for
60 minutes. During the period of the experiment the pH
value is kept constant at 9Ø
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After 60 minutes of reaction time the reaction
mixture is cooled. The content of the active substance
of this polymeric solution is 31%. The calcium binding
capacity is 520 mg of calcium carbonate per gram of
active substance. The biodegradability is 97%.
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EXAMPLE 2
One hundred-eighty grams of palatinose are
dissolved in 220 g of water and charged in a reaction
vessel. To this solution there are added 108 g of
acrylic acid and 57 g of 30% H2O2. The solution is
heated at 55 C. Then the heat supply is turned off.
The reactants are allowed to react for a period of
240 minutes with the temperature being controlled by
cooling so that the temperature rises to a maximum of
64 C. The pH value is kept constant at 8.0 during all
of the time. The content of the active substance of
this polymeric solution is 31%. The calcium binding
capacity is 520 mg of calcium carbonate per gram of
active substance. The biodegradability is 95%.
EXAMPLE 3
One hundred-eighty grams of leucrose are
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dissolved in 220 g of water and charged in a reaction
vessel. To this solution there are added 108 g of
acrylic acid and 57 g of 30% H2O2. The solution is
heated at from 60 C to 65 C with stirring. Then the
heat supply is stopped. Due to the exothermal reaction,
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1 323627
- 6 -
the temperature rises to 80 C, whereupon by cooling the
temperature is kept to remain constant at 80 C for
60 minutes. During the period of the experiment the pH
value is kept constant at 9Ø After 60 minutes time of
reaction the reaction mixture is cooled. The content of
the active substance of this polymeric solution is 31%.
The calcium binding capacity is 520 mg of calcium carb-
onate per gram of active substance. The biodegradabili-
ty is 97%.
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