CA1323627C - Copolymers of unsaturated carboxylic acids and use thereof - Google Patents
Copolymers of unsaturated carboxylic acids and use thereofInfo
- Publication number
- CA1323627C CA1323627C CA000608933A CA608933A CA1323627C CA 1323627 C CA1323627 C CA 1323627C CA 000608933 A CA000608933 A CA 000608933A CA 608933 A CA608933 A CA 608933A CA 1323627 C CA1323627 C CA 1323627C
- Authority
- CA
- Canada
- Prior art keywords
- carboxylic acids
- unsaturated carboxylic
- copolymers
- palatinose
- leucrose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Saccharide Compounds (AREA)
Abstract
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.
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.
Description
,~
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.
,, , , ' ' ~, ' ' ' ,,, . " .
-` 1 323627 .~
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.
?
The usable unsaturated carboxylic acids again include, in the first place, the monoethylenically unsaturated monocarboxylic acids having from 3 to 10 ) "
.. . . . . .
, ~ . .
~,, . ,. ,.. ,.. .. , ,. :
., , .
~ 3 6 2 7 ':, ~; carbon atoms, and preferably acrylic acid and ; 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.
`~ 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 'i .
; ~B
"~ .
~, .
,, , ;~ :
-` 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, ;
.
' . .
J
S, ~
.
i ' ' ' ' :; ' ' :' ~
~',` ~ . ': :
`_ ` ' ` '~ ' ` ' ' : ' ' : `
' ' ' ," ' ` ': I . ' , " :' " ~ ~
~ ` -` 1 323627 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
, 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%.
. ,, 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%.
One hundred-eighty grams of leucrose 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 from 60 C to 65 C with stirring. Then the heat supply is stopped. Due to the exothermal reaction, ,, .
,, : . :
`: :
~, . .
.. ..
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%.
.
) ~, ,~
'6 ' ,' ~j :
, ............................... . . .
' ' , ' ' . :
~ ' ''. ' ' ~ . ., '
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.
,, , , ' ' ~, ' ' ' ,,, . " .
-` 1 323627 .~
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.
?
The usable unsaturated carboxylic acids again include, in the first place, the monoethylenically unsaturated monocarboxylic acids having from 3 to 10 ) "
.. . . . . .
, ~ . .
~,, . ,. ,.. ,.. .. , ,. :
., , .
~ 3 6 2 7 ':, ~; carbon atoms, and preferably acrylic acid and ; 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.
`~ 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 'i .
; ~B
"~ .
~, .
,, , ;~ :
-` 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, ;
.
' . .
J
S, ~
.
i ' ' ' ' :; ' ' :' ~
~',` ~ . ': :
`_ ` ' ` '~ ' ` ' ' : ' ' : `
' ' ' ," ' ` ': I . ' , " :' " ~ ~
~ ` -` 1 323627 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
, 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%.
. ,, 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%.
One hundred-eighty grams of leucrose 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 from 60 C to 65 C with stirring. Then the heat supply is stopped. Due to the exothermal reaction, ,, .
,, : . :
`: :
~, . .
.. ..
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%.
.
) ~, ,~
'6 ' ,' ~j :
, ............................... . . .
' ' , ' ' . :
~ ' ''. ' ' ~ . ., '
Claims (6)
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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3834237A DE3834237A1 (en) | 1987-05-02 | 1988-10-07 | COPOLYMERISATE OF UNSATURATED CARBONIC ACIDS AND THEIR USE |
| DEP3834237.5 | 1988-10-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1323627C true CA1323627C (en) | 1993-10-26 |
Family
ID=6364642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000608933A Expired - Fee Related CA1323627C (en) | 1988-10-07 | 1989-08-22 | Copolymers of unsaturated carboxylic acids and use thereof |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0364681B1 (en) |
| JP (1) | JPH02151611A (en) |
| AT (1) | ATE97140T1 (en) |
| CA (1) | CA1323627C (en) |
| DE (1) | DE58906163D1 (en) |
| MX (1) | MX169863B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4344029A1 (en) * | 1993-12-23 | 1995-06-29 | Grillo Werke Ag | Copolymers of unsaturated carboxylic acids, process for their preparation and their use |
| DE19614628A1 (en) * | 1996-04-13 | 1997-10-16 | Cht R Beitlich Gmbh | Pretreatment of textiles |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1275619A (en) * | 1968-09-04 | 1972-05-24 | Int Minerals & Chem Corp | A process for preparing graft copolymers of acrylic acid with polyhydroxy polymeric compounds and the graft copolymers thereof |
| EP0289895B2 (en) * | 1987-05-02 | 1999-10-13 | Grillo-Werke Ag | Copolymers of unsaturated carboxylic acids, their preparation and their use |
-
1989
- 1989-08-03 DE DE89114318T patent/DE58906163D1/en not_active Expired - Fee Related
- 1989-08-03 EP EP89114318A patent/EP0364681B1/en not_active Expired - Lifetime
- 1989-08-03 AT AT89114318T patent/ATE97140T1/en not_active IP Right Cessation
- 1989-08-22 CA CA000608933A patent/CA1323627C/en not_active Expired - Fee Related
- 1989-09-26 MX MX017694A patent/MX169863B/en unknown
- 1989-10-06 JP JP1260315A patent/JPH02151611A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE58906163D1 (en) | 1993-12-16 |
| ATE97140T1 (en) | 1993-11-15 |
| MX169863B (en) | 1993-07-28 |
| EP0364681A2 (en) | 1990-04-25 |
| JPH02151611A (en) | 1990-06-11 |
| EP0364681A3 (en) | 1990-09-05 |
| EP0364681B1 (en) | 1993-11-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |