CA2000418A1 - Absorbing polymer - Google Patents
Absorbing polymerInfo
- Publication number
- CA2000418A1 CA2000418A1 CA002000418A CA2000418A CA2000418A1 CA 2000418 A1 CA2000418 A1 CA 2000418A1 CA 002000418 A CA002000418 A CA 002000418A CA 2000418 A CA2000418 A CA 2000418A CA 2000418 A1 CA2000418 A1 CA 2000418A1
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- absorbing
- copolymer
- weight
- acid
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/225—Mixtures of macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
Abstract
Abstract Absorbing polymer consisting of a polymer A which is an optionally modified polyvinyl alcohol or an optionally modified polysaccharide or a mixture of these, and of a polymer B which is a maleic anhydride homo- or copolymer having a hydrolysis time of 5 to 120 minutes, the anhydride groups being open and 0.005 to 5 mol % of the acid functions being esterified with hydroxyl groups of polymer A, and the remaining acid functions being present as free acid groups, as salts or as acid amide groups, an absorbing product containing this polymer and a process for their preparation.
Description
Absorbing polymer The invention relates to a novel, absorbing polymer and to an absorbing product con-taining the former, to a process for their preparation and to their use for taking up and retaining water or aqueous ~olutions.
Ab~orbing polymers usually conRist of polymers or copolymers which are hydrophilic and which have been rendered water-in~oluble by reaction wi`th suitable crosslinking agents. Such materials can absorb and hold liquid~ or steam, ~o that they are most widely used in a wide range of fields, but in particular in the sanitary sector. In connection with a ~upport, they are employed in all situations where liguids are to be removed rapidly, that is to ~ay, for example, in tissue papers, nappies, tampons, banda~es etc. On the other hand, such polymers can also be used with good success for retaining and later releasing moisture in the agricultural sector, but also in many other areas. There has therefore been no lack of attempts to provide such polymers.
For example, in DE-A-2,923,435 there i8 disclosed a process for the preparation of a crosslinked polyvinyl alcohol (PVAL), in ~S-A-3.9S6-44~ a process for the preparation of cro~slinked cellulo~e, in GB-A-2027714 a proces~ for the preparation of crosslinked carboxyalkyl cellulose and in GB-A-1,508,123 a proces~ for the prepar-ation of croeslinked starch having absorbing properties.
Besides the fact that these crosglinked hydrophilic polym~rs often contain a high proportion of watsr-soluble products, the crosslinking agents employed are poisonous monomers containing epoxy, halogen or acrylic groups.
Since the crosslinked, polymeric materials always contain a certain amount of still unreacted, monomeric cros31ink-ing agents, their use in particular in the ~anitary sector can cau~e effects which are in~urious to health.
US-A-4,332,917 describes the preparation of a polymer alloy of an MA/styrene copolymer and a cellulo~e ester in an organic solvent. For this purpose, the maleic , : .. ~ : ~
:, .: . :
,' ',"'- ..: ~
- - ~ , ~ ' ., , ' ' - . ,. : ~ . ~
ZQ~04~
anhydride groups are at least partially hydrolized, the two polymers are mixed in an organic sol~ent, and the solvent is evaporated. In EP-A-0,210,754 there i8 de-scribed a composition of polyalkylene oxides with copoly-mers which consi~t of units of an alpha-beta unsaturated monomer and a monomer which i~ copolymerizable with the former, for the preparation of a water-absorbing composi-tion. However, in both cases the specific polymers are only held together via hydrogen bond~.
From GB-A-1392624 it is known to crosslink polyethylene oxide with water-~oluble polymerS
- with the aid of ionizing radiation. However, plants which make possible the irradiation of substrate~
with ionizing radiation require complicated equipment and extensive protective measures.
Unexpectedly, it was possible with the aid of the present invention to prepare an ab~orbing polymer ~hich overcome~ the disadvantages associated with the abovementioned polymers --- and their preparation.
Accordingly, the invention relates to an absorb-inq polymer consisting of a polymer A and a polymer B, comprising polymer A~ present in an amount of 10 to 99 percent by weight and~ an optionally modified polyvinyl alcohol or an optionally modified polysaccharide or a mixture of these, and polymer B~ present in an amount of 1 to 90 percent by weight and ~ a maleic anhydride homo- or copolymer having a hydroly~i~ time of 5 to 120- minute~, the an-hydride groups being opened and 0.005 to 5 % of the acid functions being e~terified with the hydroxyl groups of ~olymer A and the remaining acid functions being present as free acid groups, as salts or as acid amide groups.
Polymar A is an optionally modified polyvinyl alcohol (PVAL) or an optionally modified polysaccharide or a mixture of such polymers. PVAh is taken to mean conventional polyvinyl alcohols having molecular weights of about 10000 to 100000. Modified PVAL means that some of the hydroxyl groups of the PVAL are present in an -` 2(~0Q4~3 esterified or etherified form. Esterified PVAL is under-stood as meaning either partially hydrolyzed polyvinyl acetate or completely or partially hydrolyzed polyvinyl acetate which is re-esterified. Compounds which are S suitable for esterifying PVAL are, for example, reactive derivatives of di- or tricarboxylic acids, such as, for example, acid anhydride~ of succinic acid, maleic acid, fumaric acid, itaconic acid or pyromellitic acid. The degree of sub~titution DS after the esterification is - 0.005 to 0.5, preferably 0.01 to 0.3. Such products are commercially available or they can be prepared by a conventional esterification method, for example with the aid of a reactive ~arboxylic!acid derivative, if appro-priate in a diluent, using basic or acid catalysts.
lS Compounds which are suitable for etherification are aliphatic or araliphatic sulphonic acids, phosphonic acids, carboxylic acids or their salts, and also quatern-ary ammonium salts having an aliphatic ~ide chain, and in which this side chain carries a rea~tive leaving group or epoxy group and can, if appropriate, al80 be substituted by hydroxyl groups. Examples of such compounds are Na 3-chloro-2-hydroxypropanesulphonate, chloromethylsulphonic acid, Na chloromethylphosphonate, Na monochloroacetate or glycidyltrimethyl~mmonium chloride. The degree of substi-tution DS after etherification is 0.005 to 0.5, prefer-ably O.01 to 0.3. Such products are commercially avail-able or they can be prepared under conventional etherif-ication conditions, in which process the reactive leaving group of the compound employed for etherification and the hydrogen ion from the hydroxyl group of the PVAL are eliminated, if appropriate in a solvent in the presence of a base, this resulting in the formation of an ether bond. In the event that an epoxy group is present in the place of a reactive leaving group, etherification takes place with basic catalysis, in which case, after the etherification raaction, a hydroxyl group is additionally present in the alpha-position relative to the ether oxygen in the aliphatic ~ide chain of the compound used for etherification. Substances which are used for esteri-- , . . , , - : . .
- , ''' '' , ' - . ~ -:, :',, :: ~ , :
fication or etherification are known substances of organic chemistry. Preferred as the polymer A is a modified PVAL, for example a PV~L modified by e~terifi-cation with æuccinic anhydride.
Possible examples of polysaccharides are starch, dextran, xanthan, water-~oluble cellulose derivatives, such as, for example, cellulose ethers, such as hydroxy-alkylcellulose, methylcellulose, carboxylmethylcellulose and hydroxypropylcellulose or sodium alginate, guar and similar sub~tances. Modified polysaccharides are poly-saccharides in which some of the hydroxyl groups are esterified or etherified with compounds as have been described above in the case of PVALs. Nodified poly-saccharides are known and commercially available, or they can be prepared as described above in the ca~e of the modified P~ALs. Preferred polysaccharides are carboxy-methylcellulose or ~odium alginate. However, polymer A
can also be a mixture of the polymers described above.
Examples of preferred mixtures are partially hydrolyzed PVALs and carboxymethylcellulose, or partially hydrolyzed PVAL and sodium alginate. Polymer A is preferably water-soluble.
Polymer B is a maleic anhydride (NA) homo- or copolymer or a mixture of MA homo- and copolymers or a mixture of various MA copolymers, the hydrolysis time being S to 120 minutes, preferably 10 to 60 minutes.
Hydrolysis time is taken to mean the time in minutes in which the pH of a stirred dispersion of 0.2 g of polymer B in 76 ml of distilled water and 17.5 ml of 0.1 molar NaOH drops from pH 12.4 to pH 10.0 at 25C. MA
homopolymers are known and can be prepared, for example, following U;A47~716 Preferably used copolymer~ are those of MA with alkyl vinyl ether, styrene, 2-methyl-styrene, monomethoxypolyethylene glycol vinyl ethers or olefins, such as ethylene, propylene, isobutylene, etc., and similar compounds. Maleicv anhydride/msthyl vinyl ether (NA/MVE) copolymerc are particularly preferred.
Copolymers of MA with abovementioned compounds are known, or they can be prepared following conventional methods, , . . , ... . . . . . .. . . ~ . ., . ~ , . .. - ; .
. ....... .: . .
. . .. .. - ... , . .. ~.
.
.
2QQQ4~8 for example MA/monomethoxypolyethylene glycol vinyl ether copolymers by the method of Tohru Suzuki et al., Journal of Polymer Science: Polymer Chemistry Edition, Vol. 22, 1984, 2829 to 2839. Polymer B is preferably water-insol-uble.
In the absorbing polymer according to the invention, the acid anhydride groups are present in virtually completely open form and, depending on the nature and amount of the base used, a small, but im-portant proportion of ~hem i8 present a3 ester group~
occasionally as a salt and free acid group8~ and in some cases also as acid amide groups. The degree of neutraliz-ation i8 the proportion of acid functions in mol %, based on the total number of acid functions present, which is presQnt as a salt. It is about 25 to 80 %.
The proportion of polymer A in the absorbing polymer according to the invention i8 10 to 99, preferably between 40 and 95 per cent by weight; the proportion of polymer B is 1 to 90, prefer~bly 25 to 60 per cent by weight.
~he abs~ir~ polymer according to the invention has an absorption ~ acity for distilled water of at least 110 to 800 g~g of dry absorbing polymer an absorE~tion capacity for a 0.9 percent ~trength aquQous NaCl solution or for an aqueous CIPAC-D standard ~olu- -tion, that is an aqueous solution having a defined ion ~ontent, which 18 described in ~xt~ple 1 of the pre~ent application, of 10 to 120 g/g of dry absorbing polymer It i~ capable of absorption over a wide temper-ature range which embraces the conventional application range of about 0 to 50C, and it is stable in the presence of those liquids which it is to absorb, which, besides water, can also be, for example, blood, urine, perspira-tion, ~ecretion of wound~, etc. A particular advantage is the fact that it is non-poisonou~.
The invention al~o relates to a proces~ for the preparation of an abgorbing po~ er, comprising combining - -an optionally modified polyvinyl alcohol, an optionally modified polysaccharide or mix-2Q~Q41~
tures of these with a maleic anhydride homo-or copolymer having a hydrolysis time of 5 to 120 min-utes, and the mixture~ treated at a temperature of 20 to 120C with 0.5 to 1.6 equivalents, added all at once, S of an inorganic or organic base per equivalent of maleic anhydride.
The preparation of the absorbing polymer:~
according to the invention can be continuous or batchwise, and, in a first step, polymer A and polymer B
are mixed in a solid, dissolved or dispersed form.
Suitable diluents or solvents are organic 801vent8 which are inert under the reaction conditions or water, water being preferred. In a preferred procedure, polymer A is dissolved in water and polymer B is added in the form of a powder or dispersed in water. The two polymer systems are combined and if appropriate heated, or the polymer systems A and B are heated before they are combined. The reaction mixture i8 treated with an inor~anic or organic base at temperatures of 20 to 120C, preferably at tem-perat~-res of about 50 to 90C. Inorganic base~ which can be employed are, for example, alkali metal hydroxides, alkali metal hydrogen carbonates, alkali metal carbon-ates, ammonia, ammonium hydro~en c~rbonate or ammonium carbonate, organic ba~es which can be employed are, for example, amines, such as methylamine, ethylamine, guan-idine carbonate etc. The base is preferably employed in the form of aqueous solutions. It is essential for the process that the base i8 added all at once, that is to say, rapidly and without interruption.
In general, the solutions or dispersions of polymers A and B are employed as concentrated as pos-~ible. When the base i8 added to the reaction mixture of polymers A and B, virtually all maleic anhydride groups of polymer B are opened, and 0.005 to 5 mol % of the acid functions formed as a result of the reaction form an ester bond with the hydroxyl groupa of polym~r A. This results in a network of polymers A and B which is bonded via covalent bonds and which has a small but Lmportant proportion of covalent ester bonds. The number of the .. , . . . ,,, , , , . , . . ................ ~ . .... . . . . .
. : :
2t~4~8 _ 7 _ covalent ester bonds in the absorbing polymer was determined photometrically via dinitrophenyl hydrazide, which absorbs at 340 nm. After the reaction, some of the acid functions are in the form of a salt and S some in the form of a free acid; if ammonia or amines are used, amide bonds can additionally al80 be formed.
Polymer A and polymer B are employed in a ratio by weight of 10:90 to 99:1, preferably of about 40:60 to about 95:5. O.5 to 1.6 equivalents of the base are used per equivalent of maleic anhydride in polymer B, 80 that after the reaction 25 to 80 % of the acid function3 are present as a sal~ and 0 to 50 % as an amide. The remain-ing acid functions, which are not pre~ent in the form of esters, amides or salts, are present in the form of free acid groups.
The reaction time i8 very short. The rate at which the reaction proceeds depends on the nature and concentration of the specifically employed starting substances, but in particular on the reaction temper-ature. At room temperature, the reaction proceeds withinminutes, at higher temperatures within saconds.
In the course of the reaction, the viscosity of the reaction mixture ~ncreases greatly. Comparison experiments have revealed that this can partly be attrib-uted to ~intertwiningN of the polymer~ A and B, asdescribed in US-A-4,169,818, but, as an important fea-ture, also to moderate esterification of polymers A and B. To this end, raaction mixture~ according to the invention and comparison reaction mixtures were prepared under identical conditions in each case. ~he only diffe-rence between these reaction mixtures was that, in the comparison case, the anhydride groups of polymer B had already been completely hydrolyzed before the ba3e was added, 80 that esterification with polymer A wa~ no longer possible. When the vi3co~ities are compared, it becomes evident that the viscosity of the reaction mix-tures according to the invention i8 substantially higher than the viscosity of the comparison reaction mixtures.
~his can only be explained by the pre~ence of ester bonds - ... . . ,- , ~
. .
- . ., . .: . ..
: - , . . . - . .: . . - , ~ - . . . . . . . . ..
()4~8 between polymer A and polymer B. ~-To obtain a dried, absorbing polymer acc ~ nq-co ~e in~enti~n, the gel formed in the reaction is applied, for -~
example, to a suitable support surface, such as gla~s, plastic or steel, dried by customary methods, such as, for example, heating, drying in the air, drying in vacuo or lyophilization, peeled off the support surface and used as a foil, or scraped off and comminuted by pounding or grinding so that the absorbing polymer is then present in the form of a film, powder or flakes and is ready for use.
Depending on the field of application, a range of ~ubstances such as softeners, surface-active substances, fillers, pigments, W-absorbing materials, antioxidants, lS odour-imparting substances, disinfectants and also chemicals suitable for agriculture can be admixed to the dried absorbing polymer or to a dispersion or solu-tion of the absorbing polymer~,... according to the invention, with the proviso that they do not negatively influence the absorption properties of the absorbing polymer according to the invention.
The absorbing polymer according to the invention can be readily and rapidly prepared, it is virtually water-insoluble, it i~ non-poisonous, has very good absorption properties, and thus repressnts an enrichment of the art. Accordingly, the absor~ing polymer according to the invention can be uYed in the form of a powder or individual pieces, in the form of foils, fibres, sheet-like structures and similar shapes, for ~ range of purpose~. Foils made of the absorbing polymer according to the invention can be used, for example, to construct moisture barrier~ in the soil. A
powder which consists of the absorbing polymer according to the invention, and which can be mi~ed for exampls with soil, gla3s beads, foamed polymers, calcined clay or comminuted plastic, improve~ the water retention properties of the soil. It is also possible to incorpor-ate active substances into the absorbing polymer according to the invention in any customary manner, thu~
:. . . . . .. . . .
: - .:
- ~ . .: .. .
, ... .
2QOQ4~3 g guaranteeing long-term effectiveness of these active substances.
Furthermore, the absorbing polymer can be combined with onP or more supports to give an absorbing product.
Supports which are possible are, for example, fibrous supports, such as woven or unwoven material, such as, for example, cotton tissue, rayon, wool, dre~sing gauze, paper or cellulose fluff, for example in the form of lengths, sheets or loose fibres, preferably lengths of paper; glass, ceramics or metal, but also materials such as wood, stone or concrete, are also possible.
The absorbing polymer ., can be applied to the support on one side or both sides, or incorporated and/or applied between several identical or different supports, 80 that laminates are present which have two or more layers of the absorbing polymer or it is present in connection with loose fibres, such as, for e~ample, cellulose fibre~, asbestos fibres or other material, in which case it can be encased between cover sheets, for example of fabric, fleece fabric or paper. It can be applied to the support continuously or batchwise, that i8 to say, in the form of, for example, strips, dots, lat-tices etc., or it can be incorporated between 2 or more supports.
Products which are preferred are, for example, products which are u~ed in the sanitary sector, such as, for example, household and industrial tissues, for example, tissue papers , ~anitary towels, tampons, surgi-30 cal spongas or swabs, facal ti~sues, bandages, swathesetc.
Such absorbing products can be prepared in various manners. The support can be immersed into a di~per~ion of the absorbing polymer -- according to the invention in a conventional manner and dried, the disper-sion can be sprayed onto the support or supports, or the absorbing polymer . is scattered onto the support in the form of a powder and adhesively bonded with the support by suitable measures, such a~, for . .
- ~ . . . . . . .
. . , .. ~ : ~ , .
Ab~orbing polymers usually conRist of polymers or copolymers which are hydrophilic and which have been rendered water-in~oluble by reaction wi`th suitable crosslinking agents. Such materials can absorb and hold liquid~ or steam, ~o that they are most widely used in a wide range of fields, but in particular in the sanitary sector. In connection with a ~upport, they are employed in all situations where liguids are to be removed rapidly, that is to ~ay, for example, in tissue papers, nappies, tampons, banda~es etc. On the other hand, such polymers can also be used with good success for retaining and later releasing moisture in the agricultural sector, but also in many other areas. There has therefore been no lack of attempts to provide such polymers.
For example, in DE-A-2,923,435 there i8 disclosed a process for the preparation of a crosslinked polyvinyl alcohol (PVAL), in ~S-A-3.9S6-44~ a process for the preparation of cro~slinked cellulo~e, in GB-A-2027714 a proces~ for the preparation of crosslinked carboxyalkyl cellulose and in GB-A-1,508,123 a proces~ for the prepar-ation of croeslinked starch having absorbing properties.
Besides the fact that these crosglinked hydrophilic polym~rs often contain a high proportion of watsr-soluble products, the crosslinking agents employed are poisonous monomers containing epoxy, halogen or acrylic groups.
Since the crosslinked, polymeric materials always contain a certain amount of still unreacted, monomeric cros31ink-ing agents, their use in particular in the ~anitary sector can cau~e effects which are in~urious to health.
US-A-4,332,917 describes the preparation of a polymer alloy of an MA/styrene copolymer and a cellulo~e ester in an organic solvent. For this purpose, the maleic , : .. ~ : ~
:, .: . :
,' ',"'- ..: ~
- - ~ , ~ ' ., , ' ' - . ,. : ~ . ~
ZQ~04~
anhydride groups are at least partially hydrolized, the two polymers are mixed in an organic sol~ent, and the solvent is evaporated. In EP-A-0,210,754 there i8 de-scribed a composition of polyalkylene oxides with copoly-mers which consi~t of units of an alpha-beta unsaturated monomer and a monomer which i~ copolymerizable with the former, for the preparation of a water-absorbing composi-tion. However, in both cases the specific polymers are only held together via hydrogen bond~.
From GB-A-1392624 it is known to crosslink polyethylene oxide with water-~oluble polymerS
- with the aid of ionizing radiation. However, plants which make possible the irradiation of substrate~
with ionizing radiation require complicated equipment and extensive protective measures.
Unexpectedly, it was possible with the aid of the present invention to prepare an ab~orbing polymer ~hich overcome~ the disadvantages associated with the abovementioned polymers --- and their preparation.
Accordingly, the invention relates to an absorb-inq polymer consisting of a polymer A and a polymer B, comprising polymer A~ present in an amount of 10 to 99 percent by weight and~ an optionally modified polyvinyl alcohol or an optionally modified polysaccharide or a mixture of these, and polymer B~ present in an amount of 1 to 90 percent by weight and ~ a maleic anhydride homo- or copolymer having a hydroly~i~ time of 5 to 120- minute~, the an-hydride groups being opened and 0.005 to 5 % of the acid functions being e~terified with the hydroxyl groups of ~olymer A and the remaining acid functions being present as free acid groups, as salts or as acid amide groups.
Polymar A is an optionally modified polyvinyl alcohol (PVAL) or an optionally modified polysaccharide or a mixture of such polymers. PVAh is taken to mean conventional polyvinyl alcohols having molecular weights of about 10000 to 100000. Modified PVAL means that some of the hydroxyl groups of the PVAL are present in an -` 2(~0Q4~3 esterified or etherified form. Esterified PVAL is under-stood as meaning either partially hydrolyzed polyvinyl acetate or completely or partially hydrolyzed polyvinyl acetate which is re-esterified. Compounds which are S suitable for esterifying PVAL are, for example, reactive derivatives of di- or tricarboxylic acids, such as, for example, acid anhydride~ of succinic acid, maleic acid, fumaric acid, itaconic acid or pyromellitic acid. The degree of sub~titution DS after the esterification is - 0.005 to 0.5, preferably 0.01 to 0.3. Such products are commercially available or they can be prepared by a conventional esterification method, for example with the aid of a reactive ~arboxylic!acid derivative, if appro-priate in a diluent, using basic or acid catalysts.
lS Compounds which are suitable for etherification are aliphatic or araliphatic sulphonic acids, phosphonic acids, carboxylic acids or their salts, and also quatern-ary ammonium salts having an aliphatic ~ide chain, and in which this side chain carries a rea~tive leaving group or epoxy group and can, if appropriate, al80 be substituted by hydroxyl groups. Examples of such compounds are Na 3-chloro-2-hydroxypropanesulphonate, chloromethylsulphonic acid, Na chloromethylphosphonate, Na monochloroacetate or glycidyltrimethyl~mmonium chloride. The degree of substi-tution DS after etherification is 0.005 to 0.5, prefer-ably O.01 to 0.3. Such products are commercially avail-able or they can be prepared under conventional etherif-ication conditions, in which process the reactive leaving group of the compound employed for etherification and the hydrogen ion from the hydroxyl group of the PVAL are eliminated, if appropriate in a solvent in the presence of a base, this resulting in the formation of an ether bond. In the event that an epoxy group is present in the place of a reactive leaving group, etherification takes place with basic catalysis, in which case, after the etherification raaction, a hydroxyl group is additionally present in the alpha-position relative to the ether oxygen in the aliphatic ~ide chain of the compound used for etherification. Substances which are used for esteri-- , . . , , - : . .
- , ''' '' , ' - . ~ -:, :',, :: ~ , :
fication or etherification are known substances of organic chemistry. Preferred as the polymer A is a modified PVAL, for example a PV~L modified by e~terifi-cation with æuccinic anhydride.
Possible examples of polysaccharides are starch, dextran, xanthan, water-~oluble cellulose derivatives, such as, for example, cellulose ethers, such as hydroxy-alkylcellulose, methylcellulose, carboxylmethylcellulose and hydroxypropylcellulose or sodium alginate, guar and similar sub~tances. Modified polysaccharides are poly-saccharides in which some of the hydroxyl groups are esterified or etherified with compounds as have been described above in the case of PVALs. Nodified poly-saccharides are known and commercially available, or they can be prepared as described above in the ca~e of the modified P~ALs. Preferred polysaccharides are carboxy-methylcellulose or ~odium alginate. However, polymer A
can also be a mixture of the polymers described above.
Examples of preferred mixtures are partially hydrolyzed PVALs and carboxymethylcellulose, or partially hydrolyzed PVAL and sodium alginate. Polymer A is preferably water-soluble.
Polymer B is a maleic anhydride (NA) homo- or copolymer or a mixture of MA homo- and copolymers or a mixture of various MA copolymers, the hydrolysis time being S to 120 minutes, preferably 10 to 60 minutes.
Hydrolysis time is taken to mean the time in minutes in which the pH of a stirred dispersion of 0.2 g of polymer B in 76 ml of distilled water and 17.5 ml of 0.1 molar NaOH drops from pH 12.4 to pH 10.0 at 25C. MA
homopolymers are known and can be prepared, for example, following U;A47~716 Preferably used copolymer~ are those of MA with alkyl vinyl ether, styrene, 2-methyl-styrene, monomethoxypolyethylene glycol vinyl ethers or olefins, such as ethylene, propylene, isobutylene, etc., and similar compounds. Maleicv anhydride/msthyl vinyl ether (NA/MVE) copolymerc are particularly preferred.
Copolymers of MA with abovementioned compounds are known, or they can be prepared following conventional methods, , . . , ... . . . . . .. . . ~ . ., . ~ , . .. - ; .
. ....... .: . .
. . .. .. - ... , . .. ~.
.
.
2QQQ4~8 for example MA/monomethoxypolyethylene glycol vinyl ether copolymers by the method of Tohru Suzuki et al., Journal of Polymer Science: Polymer Chemistry Edition, Vol. 22, 1984, 2829 to 2839. Polymer B is preferably water-insol-uble.
In the absorbing polymer according to the invention, the acid anhydride groups are present in virtually completely open form and, depending on the nature and amount of the base used, a small, but im-portant proportion of ~hem i8 present a3 ester group~
occasionally as a salt and free acid group8~ and in some cases also as acid amide groups. The degree of neutraliz-ation i8 the proportion of acid functions in mol %, based on the total number of acid functions present, which is presQnt as a salt. It is about 25 to 80 %.
The proportion of polymer A in the absorbing polymer according to the invention i8 10 to 99, preferably between 40 and 95 per cent by weight; the proportion of polymer B is 1 to 90, prefer~bly 25 to 60 per cent by weight.
~he abs~ir~ polymer according to the invention has an absorption ~ acity for distilled water of at least 110 to 800 g~g of dry absorbing polymer an absorE~tion capacity for a 0.9 percent ~trength aquQous NaCl solution or for an aqueous CIPAC-D standard ~olu- -tion, that is an aqueous solution having a defined ion ~ontent, which 18 described in ~xt~ple 1 of the pre~ent application, of 10 to 120 g/g of dry absorbing polymer It i~ capable of absorption over a wide temper-ature range which embraces the conventional application range of about 0 to 50C, and it is stable in the presence of those liquids which it is to absorb, which, besides water, can also be, for example, blood, urine, perspira-tion, ~ecretion of wound~, etc. A particular advantage is the fact that it is non-poisonou~.
The invention al~o relates to a proces~ for the preparation of an abgorbing po~ er, comprising combining - -an optionally modified polyvinyl alcohol, an optionally modified polysaccharide or mix-2Q~Q41~
tures of these with a maleic anhydride homo-or copolymer having a hydrolysis time of 5 to 120 min-utes, and the mixture~ treated at a temperature of 20 to 120C with 0.5 to 1.6 equivalents, added all at once, S of an inorganic or organic base per equivalent of maleic anhydride.
The preparation of the absorbing polymer:~
according to the invention can be continuous or batchwise, and, in a first step, polymer A and polymer B
are mixed in a solid, dissolved or dispersed form.
Suitable diluents or solvents are organic 801vent8 which are inert under the reaction conditions or water, water being preferred. In a preferred procedure, polymer A is dissolved in water and polymer B is added in the form of a powder or dispersed in water. The two polymer systems are combined and if appropriate heated, or the polymer systems A and B are heated before they are combined. The reaction mixture i8 treated with an inor~anic or organic base at temperatures of 20 to 120C, preferably at tem-perat~-res of about 50 to 90C. Inorganic base~ which can be employed are, for example, alkali metal hydroxides, alkali metal hydrogen carbonates, alkali metal carbon-ates, ammonia, ammonium hydro~en c~rbonate or ammonium carbonate, organic ba~es which can be employed are, for example, amines, such as methylamine, ethylamine, guan-idine carbonate etc. The base is preferably employed in the form of aqueous solutions. It is essential for the process that the base i8 added all at once, that is to say, rapidly and without interruption.
In general, the solutions or dispersions of polymers A and B are employed as concentrated as pos-~ible. When the base i8 added to the reaction mixture of polymers A and B, virtually all maleic anhydride groups of polymer B are opened, and 0.005 to 5 mol % of the acid functions formed as a result of the reaction form an ester bond with the hydroxyl groupa of polym~r A. This results in a network of polymers A and B which is bonded via covalent bonds and which has a small but Lmportant proportion of covalent ester bonds. The number of the .. , . . . ,,, , , , . , . . ................ ~ . .... . . . . .
. : :
2t~4~8 _ 7 _ covalent ester bonds in the absorbing polymer was determined photometrically via dinitrophenyl hydrazide, which absorbs at 340 nm. After the reaction, some of the acid functions are in the form of a salt and S some in the form of a free acid; if ammonia or amines are used, amide bonds can additionally al80 be formed.
Polymer A and polymer B are employed in a ratio by weight of 10:90 to 99:1, preferably of about 40:60 to about 95:5. O.5 to 1.6 equivalents of the base are used per equivalent of maleic anhydride in polymer B, 80 that after the reaction 25 to 80 % of the acid function3 are present as a sal~ and 0 to 50 % as an amide. The remain-ing acid functions, which are not pre~ent in the form of esters, amides or salts, are present in the form of free acid groups.
The reaction time i8 very short. The rate at which the reaction proceeds depends on the nature and concentration of the specifically employed starting substances, but in particular on the reaction temper-ature. At room temperature, the reaction proceeds withinminutes, at higher temperatures within saconds.
In the course of the reaction, the viscosity of the reaction mixture ~ncreases greatly. Comparison experiments have revealed that this can partly be attrib-uted to ~intertwiningN of the polymer~ A and B, asdescribed in US-A-4,169,818, but, as an important fea-ture, also to moderate esterification of polymers A and B. To this end, raaction mixture~ according to the invention and comparison reaction mixtures were prepared under identical conditions in each case. ~he only diffe-rence between these reaction mixtures was that, in the comparison case, the anhydride groups of polymer B had already been completely hydrolyzed before the ba3e was added, 80 that esterification with polymer A wa~ no longer possible. When the vi3co~ities are compared, it becomes evident that the viscosity of the reaction mix-tures according to the invention i8 substantially higher than the viscosity of the comparison reaction mixtures.
~his can only be explained by the pre~ence of ester bonds - ... . . ,- , ~
. .
- . ., . .: . ..
: - , . . . - . .: . . - , ~ - . . . . . . . . ..
()4~8 between polymer A and polymer B. ~-To obtain a dried, absorbing polymer acc ~ nq-co ~e in~enti~n, the gel formed in the reaction is applied, for -~
example, to a suitable support surface, such as gla~s, plastic or steel, dried by customary methods, such as, for example, heating, drying in the air, drying in vacuo or lyophilization, peeled off the support surface and used as a foil, or scraped off and comminuted by pounding or grinding so that the absorbing polymer is then present in the form of a film, powder or flakes and is ready for use.
Depending on the field of application, a range of ~ubstances such as softeners, surface-active substances, fillers, pigments, W-absorbing materials, antioxidants, lS odour-imparting substances, disinfectants and also chemicals suitable for agriculture can be admixed to the dried absorbing polymer or to a dispersion or solu-tion of the absorbing polymer~,... according to the invention, with the proviso that they do not negatively influence the absorption properties of the absorbing polymer according to the invention.
The absorbing polymer according to the invention can be readily and rapidly prepared, it is virtually water-insoluble, it i~ non-poisonous, has very good absorption properties, and thus repressnts an enrichment of the art. Accordingly, the absor~ing polymer according to the invention can be uYed in the form of a powder or individual pieces, in the form of foils, fibres, sheet-like structures and similar shapes, for ~ range of purpose~. Foils made of the absorbing polymer according to the invention can be used, for example, to construct moisture barrier~ in the soil. A
powder which consists of the absorbing polymer according to the invention, and which can be mi~ed for exampls with soil, gla3s beads, foamed polymers, calcined clay or comminuted plastic, improve~ the water retention properties of the soil. It is also possible to incorpor-ate active substances into the absorbing polymer according to the invention in any customary manner, thu~
:. . . . . .. . . .
: - .:
- ~ . .: .. .
, ... .
2QOQ4~3 g guaranteeing long-term effectiveness of these active substances.
Furthermore, the absorbing polymer can be combined with onP or more supports to give an absorbing product.
Supports which are possible are, for example, fibrous supports, such as woven or unwoven material, such as, for example, cotton tissue, rayon, wool, dre~sing gauze, paper or cellulose fluff, for example in the form of lengths, sheets or loose fibres, preferably lengths of paper; glass, ceramics or metal, but also materials such as wood, stone or concrete, are also possible.
The absorbing polymer ., can be applied to the support on one side or both sides, or incorporated and/or applied between several identical or different supports, 80 that laminates are present which have two or more layers of the absorbing polymer or it is present in connection with loose fibres, such as, for e~ample, cellulose fibre~, asbestos fibres or other material, in which case it can be encased between cover sheets, for example of fabric, fleece fabric or paper. It can be applied to the support continuously or batchwise, that i8 to say, in the form of, for example, strips, dots, lat-tices etc., or it can be incorporated between 2 or more supports.
Products which are preferred are, for example, products which are u~ed in the sanitary sector, such as, for example, household and industrial tissues, for example, tissue papers , ~anitary towels, tampons, surgi-30 cal spongas or swabs, facal ti~sues, bandages, swathesetc.
Such absorbing products can be prepared in various manners. The support can be immersed into a di~per~ion of the absorbing polymer -- according to the invention in a conventional manner and dried, the disper-sion can be sprayed onto the support or supports, or the absorbing polymer . is scattered onto the support in the form of a powder and adhesively bonded with the support by suitable measures, such a~, for . .
- ~ . . . . . . .
. . , .. ~ : ~ , .
2~0Q4~
example, steam and/or pressure treatment. To coat fibres, polymer A, polymer B and - all at once - the base can be incorporated into a suspension of fibres, so that the absorbing product i8 formed directly in the reaction mixture. Furthermore, it is possible to spray polymer A, polymer B and the base in solution or dispersion onto a continuously moving length of support. In this case, polymer A, polymer B and the base can be sprayed on either individually or together.
In a particularly preferred embodiment, an aqueous solution of polymer A is combined with polymer B
which is employed in the form of a powder in aqueou~
dispersion. This dispersion and the solution of the base, both of which are as concentrated as possible, are propelled through nozzles with the aid of pressurized air or steam and sprayed onto the support. In thi case, the base can be mixed with polymer A and polymer B either within the nozzle or outside the nozzle. If a length of paper i8 used as the support, and if the reaction mixture is applied in a highly concentrated form and only in small amounts, it is possible for in particular an over-dried paper to take up the entire moisture.
If the support contains free hydroxyl groups, such as, for example, in the case of cellulose-containing supports, the former can be involved in the crosslinking proce~s 80 that particularly good bonding to the support takes place when the absorbing layer is formed.
The absorbing products ha~e excellent absorption properties, the bonding between support and polymer ~
being good and durable, and they can be pre-pared Qasily, rapidly and with a low input of energy and costs, and therefore represent an enrichment of the art.
Exa~ple 1 Maleic anhydride/methyl vinyl ether (MA~NV~ copolymer) 87.3 g of maleic anhydride and 1.46 g of di-lauroyl peroxide were introduced into a 2 1 Juchheim pre~surized reaction vessel, and the reaction apparatus wa~ then flushed with nitrogen. When the apparatus was free from oxygen, 310 g of methyl vinyl ether which had '" ' . '. ' : . ... ' , '. ' . . `. ~.' ~ . ' : :
," ' , . ' ~: '''.' ' :' '.
. '" , '' ' . ' ' " " .~ ' ' , ': ' ~: ' ' ~ ' ~, ' , ' .
.. : '' ,: ' .
ZQOQ4~L8 been dried over solid sodium hydroxide and freshly di~tilled, were added. The react.Lon mixture was warmed to 55C with stirring and maintainecl at thi~ temperature for 2 hours under pressure. After the mixture had cooled to 20C, excess methyl vinyl ether was di~tilled off, and the reaction product was removed from the ves~el. Thi~
gave 118 g (84.9 % of theory) of an MA/MV~ copolymer having the following properties: loss on drying at 105C:
0.92 %, at 60C in vacuo: 0.25 %. The particle size 10 distribution~ which was measured by sieve analysi~, gave the following values:
Particle size (micrometers) (%) below 32 43.6 32 - 44 7.6 44 - 100 13.0 100 - 200 14.0 200 - 354 14.2 354 - S00 5.8 500 - 710 0.6 710 - 850 0.6 850 - 1400 0.6 Conditionss Alpine air-~et sieve, 0.02 bar vacuum;
sieving ti~e: 7 minutes. The specific vi~cosity was determined as followss 0.5 g of MA/NVE copolymer was ~ -dissolved in 50 ml of methyl ethyl ketone and the 801u-tion was stirred for 1 to 2 hours at roo~ temperature.
The specific viscosity was measured with the aid of a Ubbelohde viscometer and was 3.2.
The hydrolysis rate of the MA groups wa~ determined as follow~.
17.5 ml of a 0.1 molar aqueous sodium hydroxide solution and 76 ml of distilled wat~r (having a pH of 12.4) w~re dispersed with 0.2 g of MA/MV~ copolymer in a 250 ml round-bottomed flask equipped with a RPG stirrer (blade diamsters 5 cm) at 250 rpm. The pH drop in the measuring apparatus was determined with the aid of a glass elec-trode. The hydrolysis time is defined as the period in minutes which i8 required for the pH to drop from pH 12.4 to pH 10Ø The hydrolysis rate was 30 minute~.
,- .- ...... . . : ~ ~
- , - .~ ......................................... . :
.. . . .. . . .
~ ~0~ ~8 Example 2 Polymer A: Polyvinyl alcohol (PVAL), Mowiol 8-88, Hoechst, FR~
Polymer B: Maleic anhydride/methyl vinyl ether (MA/MVE) copolymer of Example I
100 g of 5 % by weight aqueous solution of polymer A were heated to 80C and treated with 5 g of polymer B in the form of a powder, with stirring. 30 ml of a 1 molar aqueous sodium hydroxide solution were then added all at once, which resulted in gel formation in the reaction vessel within one minute. The gel was brushed onto a plastic foil and dried at 100C. 0.17 mol ~ of the acid functions of polymer BL were pre~ent in the form of ester~. The absorption properties of the dried gel were determined in the following manner-The dried gel was scraped off the pla~tic foil.
About 0.2 g were transferred into a teabag and immersed in an aqueous test ~olution. The test solutions used were, on the one hand, di~tilled water, on the other hand a CIPAC-D standard solution which is an aqueous solution having an exactly defined ion content (CIPAC, Handbook, Vol. 1, Analysis of Technical Formulated Pesticides, R.
Ashworth, J. Henriet, J.F. Lovett, Cellaboration Inter-national Pesticide, Analytical Cou~cil, 1970, 875 to 879), and a 0.9 % by weight NaCl olution. After 24 hours, the teabag was re~oved from the test solution, placed on a filter paper base and turned without applica-tion of pressure until the e~cape of liquid had ceased (about 4 minutes). After this, the we~ght of the swelled ~ample was determined. The absorption capacity AC of the polymerized ~ub~tance for a test ~olution wa3 calculated as follows:
AC (g/g) = Weight of the swelled sample - weight of the dry polymer ;~
Weight of the dry polymer ,, , . . .. . - . , . --, - , .
- ,: . .. .
. . :
: . ~ .: - ' 2QOQ4~
AC-D is the absorption capacity for distilled water AC-C is the absorption capacity for a CIPAC-D standard solution AC-N is the absorption capacity of a 0.9 % by weight sodium chloride solution The gel had the following absorption propertie~:
AC-D: 434 AC-C: 49 AC-Ns 49 The same procedure was also used for determining the absorption capacitie~ of the absorbing polymer in the other examples.
Example 3 Polymer A: PVAL, ~owiol 4-88, Hoechst, FRG
Polymer B: NA/MVE copolymer of Example 1 ~ 27 % by weight aqueous solution of polymer A
was introduced in a mixing vessel at a flow of 7.4 g/min together with polymer B in the form of a powder, Ln an amount of 2 g/min, and the mixture was homogenized. The .
dispersion which formed was continuously withdrawn in an amount of 9.4 g/min, heated to 80C, mixed with 4 ml/min of a 17 % by weight aqueous sodium carbonate solution, immediately sprayed onto a paper length of width 23 c.m, moving at 12.4 m/min, and dried with hot air. To measure the absorption properties of the absorbing product, batches of 3 to 7 samples in the sh~pe of circles were punched out of the coated length of paper, immersed in test solutions as described in Example 1 and then treated as in ~xample 1. The absorption capacity of the absorb~ng product for a test solution was calculated as followR:
AC (g/g) Weight of the swelled sample - weight of the w~t support ; .;
Weight of the dry sample - weight of the dry support The absorbing product had the following absorp-. . ~: .......... .. - ........ - - :: . , :
: - ~ :... . . . . . - . .. .. . . .. .. . . .
2QOQ4~3 ~ 14 -tion properties:
AC-D: 244 AC-C: 41 The same procedure was used for determining the absorption capacity of the absorbing products in the other examples.
Example 4 Polymer A: PVAL, Mowiol 4-88, Hoechst, FRG
Polymer B: MA/MVE copolymer of E~ample 1 100 g of a 24.8 ~ by weight aqueous solution of polymer A were heated to 80C and treated with 24.8 g of polymer B in the form of a powder, with stirring. After this, 39.4 g of a 20 % by weight aqueous sodium carbonate isolution were added all at once. After about 30 iseconds, the reaction mixture started foaming, this resulting in the formation of a foamed product which was brushed on and dried at 10~C.
Without support On paper AC-D: 214 203 ~C-C: 30 19 AC-N: 34 -Exa,lnDle ~
Polymer A: PVAL, Mowiol 4-88, Hoechst, FRG
Polymer B: MA/NVE copolymer of Example 1 The procedure of Example 2 was followed, but at a reaction and drying temperature of 25C, this giving 2 dried gel having the following propertie~s . .
Without support On paper AC-Ds 142 191 AC-Cs 31 25 AC-N: 38 -O.084 mol % of the acid functions of polymer B were present in the form of an ester.
.. .. - ~
~, :
2QOQ4~8 Example 6 Polymer A: PVAL, Mowiol 8-88, Hoechst, FRG
Polymer B: MA~MVE copolymer of Example 1 50 g of a 10 % by weight solution of polymer A
were warmed to 80C and treatecl with 1 g of polymer B, with stirring. After this, 30 ml of a 1 molar aqueous ammonium hydrogen carbonate solution were added all at once, which made the reaction mixture foam, and a foamed product was formed.
Without support On paper AC-D: 393 140 AC-C: 36 12 AC-N: 33 Example 7 A~ d~scribed in Example 6, but using 30 ml of a O.5 molar, aqueous guanidine carbonate solution as the base, a gel being obtained.
On paper AC-C: 24 AC-~: 34 Example 8 - Polymer As Carboxymethylcellulose tCMC), Cekol-DVEP Type, Billerud, Sweden;
Polymer B: MA/MVE copolymer of Example 1 100 g of a 5 ~ by weight solution of polymer A
were heated to 80C and treated with S g of polymer B, with stirring. A gel was formed within one minute by adding 30 ml of a 1 molar aqueous sodium hydroxide solution all at once.
!
Without support On paper AC-D: 55 65 AC-C: 64 .:
: .. .. - . . .. : ,- ., . .:.. .: . .. .. - .: ~
., . , . . . . . .. . ., . . ... . - .
- -. ~ . . ,. ~ .. . . .- . .
2QOQ4~8 Example 9 Polymer A: Sodium alginate, Protanal LF 20J60, AMEA, Austria Polymer B: MA/MVE copolymer of ]~xample 1 4.5 g of polymer A and 4.5 g of polymer B were run into 145 ml of distilled water, and the mixture was then heated to 70C with stirring. A gel was formed in the course of 2 minutes by adding 28.8 ml of a 1 molar aqueou~ sodium hydroxide solution all at once.
Without support On paper AC-D: 208 214 AC-C: 72 68 Example 10 Polymer A: Hydroxypropyl starch, Solamyl 9570, AGENA, Austria Polymer Bs MA/MYE copolymer of Bxample 1 The procedure of Example 9 was followed, but using 160 ml of distilled water, 12 g of polymer A, 6 g of polymer B and 53.8 ml of a 1 molar aqueous sodiu~ :.
hydrox~de solution.
Without support On paper AC-Ds 220 180 AC-Cs 26 - :~
Example 11 Polymer As Cold-soluble starch, Sobex 242, Sudstarke, FRG
Polymer B: MA/NVE copolymer of Example 1 The procedure of Example 9 was followed, but using 160 ml of wa~er, 6 g of poly.mer A, 3 g of polymer B and 26.9 ml of a 1 molar, aqueous sodium hydroxide solution.
Without support On paper AC-Ds 227 123 Ar-cs- 20 : . , , 2QOQ4~.8 Example 12 Polymer A: Phosphate guar, Meyprofilm 500, Meyhsll, Switzerland Polymer ~: NS/MVE copolymer of Example 1 The procedure of Example 9 was followed, but using 160 ml of water, 6 g of polymer A, 6 g of polymer B and 38.4 ml of 1 molar aqueous sodium hydroxide solu-tion.
Without support On paper AC-D: 152 215 AC-C: 18 28 AC-N: 22 Example 13 Polymer A: Depolymerized guar, Meyprogat 90, Meyhall, Switzerland Polymer B; MA/MVE copolymer of Example 1 The procedure of Example 9 was followed, but usihg 160 ml of water, 3 g of polymer A, 3 g of polymer B
and 19.2 ml of a 1 molar aqueous sodium hydroxide solution.
Without support On paper AC-Cs 25 14 ~!~
AC-Ns 12 Example 14 Polymer As Native guar, Meyproguar CSA 200/50, ~eyh~
Switzerland Pol y r B: NA/MVE copolymer of Example 1 The proce~ure of Example 9 was followed, but using 160 ml of water, 3 g of polymer A, 3 g of po~ymar and 2 6 . 9 ml o f a 1 molar aqueou~ sodium hydroxide solution. :-.
Without support AC-D: 113 AC-C: 23 AC-N: 22 .
.
.
, .
Example 15 Polymer ~: Hydroxypropyl starch, Solamyl 9570, AGENA, Austria, and PVAL, Mowiol 4-88, Hoechst, FRG, in the ratio of 1:1 Polymer B: MA/MVE copolymer of Example 1 50 g of a 5 % by weight aqueous hydroxypropyl starch solution was made into a paste and treated at room temperature with 12.5 g of a 20 % by weight PVAL solu-tion, and the mixture was heated to 80C, after which 5 g of polymer B were added with stirring. A gel was formed within one minute after 30 ml of a 1 molar aqueous ~odium hydroxide solution were added all at once.
.
Without support On paper AC-D: 308 247 AC-C: 28 22 AC-N: 32 Example 16 Polymer A: Cold-soluble starch, Sobex 242, Sudstarke, FRG, and PVAL, Mowiol 4-88, Hoechst, FRG, in the ratio by weight of 1:1 Polymer Bs NA/MVE copolymer of ~xample 1 50 g of a 5 % by weight agueous starch solution were mixed with 12.5 g of a 20 % by weight aqueous PVAL
solution, and the mixture was heated to 80C and treated with 5 g of polymer B in the form of a powder. A gel was formed after 30 ml of a 1 molar aqueou~ potassium hydrox-ide solution were added all at once.
Without support On paper AC-D: 259 138 AC-C: 28 15 AC-Ns 27 Examp~e 17 Polymer As Sodium alginate, Protanal LF 20/60, AMEA, Austria, and PVAL, Mowiol 4-88, Hoechst, FRG
Polymer B: MA-MVE copolymer of Example 1 - . .
, ~ , .
.
X~Q~8 100 ml of a 3 % by weight aqueous sodium alginate solution and 7.5 g of a 20 % by weight aqueous PVAL
solution were mixed at room temperature, and the mixture was heated to 80C and treated with 4.5 g of polymer B in the form of a powder. A gel was formed after 27 ml of a 1 molar aqueous sodium hydroxide 501ution were added all at once.
Without support On paper AC-D: 250 220 AC-C: 67 52 Example 18 The procedure of Example 17 was followed, the ratio by weight of the ~tarting 3ubstances sodium alginate:PVAL:MA/MVE copolymer being 1:1:2.
15Without support On paper AC-D: 319 277 AC-C: 52 50 Example 19 ~ he procedure of Example 17 was followed, the ratio by weight of the starting substances sodium alginate:PYAL:MA/MVE copolymer be~ng 1:0.5:1.5.
Without support On paper AC-Ds 333 236 AC-C: 48 43 Examp~e 20 Polymer A: Carboxymethylcellulose (CMC), CEROL ~ :
HDEG,Billerud, Sweden, and :
PVAL, Mowiol 4-88, Hoechst, FRG
Polymer B: MA/NVE copolymer of Example 1 3080 g of a 4 % by weight aqueous solution of CMC
and 16 g of a 20 % by weight aqueous solution of PVAL
were heated to 82C and treated with 6.4 g of polymer B
in the form of a powder. A gel was formed within 1 minute i-`
'''"
.. . ... ~................ . . . ,- ~, ., , ~ . ..
2~0Q4~8 after 38.4 ml of a 1 molar aqueous sodium hydroxide solution were added all at once.
Without support On paper AC-D: 289 383 AC-C: 64 39 AC-N: 55 Ex~nple 21 Polymer A: Hydrolyzed wheat starch, Merigum C, Amylum, Belgium, and PVAL, Mowiol 8-88, Hoechst, FRG
Polymer B: MA/MVE copolymer of Example 1 6 g of wheat starch and 6 g of PVAL were made into a paste or dissolved, respectively, in 123 ml of distilled water at 82C, after which 6 g of MA~MVE co-polymer, dispersed in 20 ml of water, were added with stirring. A gel was formed within 30 to 50 seconds after 39 ml of a 1 molar aqueous sodium hydroxide 301ution were added all at once.
Without support On paper AC-Ds 374 188 AC-C~ 18 16 AC-Ns 18 Example 22 Polymer As Cationic potato starch, Cationamyl 9852, AGENA, Austria, and xanthan gum, Jungbunzlauer, Austria, Polymer Bs NA/MVE copolymer of Example 1 6 g of potato starch and 3 g of xanthan gum were made into a paste or dissolved, respectively, in 140 ml of distilled water at 80C, and treated with 3 g of polymer B which had been dispersed in 20 ml of water. A
gel was formed within 30 second~ after 27 ml of ~ 1 molar aqueous sodium hydroxide solution were added all at once.
. - . . .
- . ,:, . . ~ . . : .
2QQQ4~3 Without support On paper AC-D: 144 113 AC-C: 19 25 AC-N: 17 Examples 23 - 27 3 g of a range of comminuted cellulose materials were incorporated in 100 g of a 5 % by weight PVAL
solution (Mowiol 8-88, Hoech~t, FRG), and the mixture was stirred to form fine fibres. This mixture was heated to 80C and treated with 8 g of MA/MVE copolymer of Example 1. A gel was formed within 20 seconds after 48 ml of a 1 molar agueous sodium hydroxide solution were added all at once.
, Example 23 Cellulose material: Photocellulose, Borregaard, Austria PVALsCellulose:MA/MVE copolymer - 1:0.6:1.6 (5 g:3 g:8 gJ
48 ml of 1 molar NaOH ::
Without ~upport On paper AC-D: 334 254 AC-C: 24 23 AC-N: 18 ,:
Exa~ple 24 Cellulose material: Sulphatecellulo~e, degre~ of freene~s 12 SR, whitene~s 88.? %, P~ls, ~ -Austria .
PVAL:CellulosesMA/MYE copolymer = 1:0.6:1.6 (5 g:3 g:8 i 48 ml of 1 molar NaOH ~:-Without support On paper AC-D: 390 256 AC-C: 25 19 AC-N: 18 - :
. . . : . .- . . :. . - . .. . . . . . ~ . . . .. : . . . .. ~ . .
200Q4~3 Example 25 Cellulose material:tissue paper- A, Zewa, PWA, FRG
PVAL:Cellulose:NA/MVE copolymer = 1:0.6:1.6 (5 g:3 g:8 g) 48 ml of 1 molar NaOH
Without support On paper ~C-D: 284 251 AC-C: 29 27 AC-N: 22 Example 26 Cellulose material tissue paper B. Henry, Laakirchen, Austria PVAL:Cellulose:MA/MVE copolymer = 1:1:2 (5 g:5 g: 10 g) 60 ml of 1 molar NaOH
' Without support On paper AC-D: 227 196 AC-C: 23 28 AC-N: 23 Example 27 Cellulose material, sulphite cellulose, fully bleached, Steyrerm~hl, Au~tria PVAL:CellulosesMa copolymer = 1:1:2 (5 g:5 g:10 g) 60 ml of 1 molar NaOH
Without support On paper AC-D: 218 204 AC-C: 20 18 AS-N: 17 0.113 mol ~ of the acid functions of polymer B were preQent in the form of esters.
Example 28 PVAL succinate 100 g of a 36 % by weight aqueous PVAL solution (Mowiol 4-88, Hoechst, FRG) were stirred with 24.5 g of succinic anhydride and O.3 g of concentrated sulphuric .....
..
2al0Q4~8 acid for 1 hour at 60C. The reaction mixture was then cooled to room temperature and added dropwise to acetone, PVAL succinate being precipitated. The precipitate wa~
filtered off, washed with acetone and dried at 50C to constant weight. Thi~ gave 4g g of PVAL succinate. ~he degree of substitution DS wa determined titrimetrically.
The degree of substitution was 0.149 mol of succinic ester groups per mol of hydroxyl groups in the PVAL.
PVAL succinateq having degrees of substitution of 0.016; 0.038; 0.091 and 0.293 mol of ~uccinic ester groups per mol of hydroxyl groups in the PVAL were prepared following the above procedure u~ing appropriate amounts of succinic anhydride.
Compounds 29 to 33 were prepared following the procedure of Ex~mple 2 and using, in each case, 5 g of PVAL succinate of the appropriate degree of substitution DS, 5 g of polymer B and 30 ml of 1 molar aqueous sodium hydroxide solution: -Example 29 - 33 Polymer A: PVAL succinate of degree of substitution DS ~ ~i Polymer B: MA/NVE copolymer of Example 1 No.DS AC-D AC-C AC-N
withoutwithout without supportsupport support 290.016 431 54 50 300.038 398 6~ 52 310.091 353 64 48 320.149 400 64 41 330.293 424 61 43 Example 34 PVAL hydroxypropane~ulphonic acid ether 100 g of a 20 % by ~eight aqueous solution of PV~L, ~owiol 8-88, Hoechst, FRG, were treated with 17.8 g of a 25 % by weight aqueous ~olution of Na 3-chloro-2-hydroxypropanesulphonate (Na CHPS), and the mixture washeated to 60C. In this process, the pH was maintained at , ~, : , ~ . : ., : :
~QOQ~:18 8 by dropwise addition of a 20 % by weight aqueous sodium hydroxide solution. When the reaction was complete, the reaction solution was added dropwise to acetone, PVAL
hydroxypropanesulphonic acid ether being precipitated.
The precipitate was filtered ffr washed with acetone and dried. This gave 21 g of PVAL hydroxypropanesulphonic acid ether. PVAL hydroxypropanesulphonic acid ethers wer~ prepared following the above procedure using ap-propriate amounts of 3-chloro-2-hydroxypropanesulphonic acid ether.
The following polymerized sub3tances were pre-pared following the procedure described in Example 2 using 120 ml of a 1 molar aqueous sodium hydroxide solution, in each case 20 g of P~AL hydroxypropane-sulphonic acid e~her as polymer A, dissolved in 80 ml of distilled water, and in each case 20 g of MA/NVE copoly-mer as polymer B, prepared in ~xample 1:
Examples 35 - 39 No. Amount of AC-D On AC-C On AC-N
NaCHPS (25 % without paper without paper without b.w.) in g support support support 35 3.57 423 347 37 36 34 36 17.84 462 293 47 30 50 37 39.59 326 245 28 20 28 38107.08 268 398 34 24 43 39278.48 337 358 34 26 35 Example 40 PVAL 2-hydroxypropane-3-(trimethylammonium chloride) ether 0.40 g of glycidyltrimethylammonium chloride were stirred into 200 ml of a 5 % by weight aqueous solution of PVAL, Mowiol 8-88, Hoechst, FRG, o~ Example 1 at room temperature, and the reaction mixture was heated to 60C
and maintained at pH 8 by continuous addition of an aqueous sodium hydroxide solution. After 2 hours, the reaction mixture was cooled to room temperature, and the . . . : . : . .: ~ ., , - , ~ , . . . . . .
~ , - . . - .
2QOQ41~3 , product formed wa~ precipitated by adding acetone, filtered off, washed and dried at 50C. This proces~ gave 10.4 g of the title compound.
Example 41 A product having the following properties was obtained following the procedure described in Example 2 and using 5 g of the product of Example 40, di~solved in 100 ml of distilled water, 5 g of MA/NVE copolymer prepared in Example 1 in the form of a powder and 30 ml 10 of a 1 molar aqueou~ sodium hydroxide solution:
Without support AC-D: 3s3 AC-C: 35 AC-N: 51 :
Exam~le 42 6 g of cationic potato starch (Amylofax 15, DS = 0.027, AVE8E, NL) and 6 g of PVAL (Mowiol 8-88, Hoechst, FRG) were made into a paste, or dissolved, respectively, in 123 ml of water at 82C, and the mixture was treated with 6 g of MA/MV~ copolymer, prepared in Example 1, ~nd di~persed in 20 ml of water. A gel was formed within ~econds after 39 ml of 1 molar aquaous sodium hydroxide solution were added all at once.
Without support On paper AC-Ds 253 159 :
AC-C: 18 16 AC-Ns 16 - .
Example 43 -~
6 g of cationic potato starch (Amylofax 15, DS = 0.027, AYEBE, NL) and 3 g of CMC (CEROL HDEG, :
Billerud, Sweden), were made into a paste, or dissolved, respectively, in 140 ml of distilled water at 80C, and the mixture was treated with an aqueous di~persion of 3 g of MA/MVE copolymer, prepared in Example 1, in 20 ml of `
.. ..
, : .: , . . ; . .
ZOOQ4~L8 water. A gel was formed within a few seconds after 27 ml of 1 molar aqueous sodium hydroxide ~olution were added all at once.
; Without support On paper AC-D: 230 156 AC-C: 32 30 ! Example 44 Polymer A: Cationic potato starch, Cationamyl 9852, AGENA, Austria Polymer B: MA/isobutylene copolymer, Isobam-10, Ruraray, Japan 6 g of polymer A were mada into a paste in 160 ml of distilled water at 70C, and the mixture was treated with stirring with 3 g of polymer B which had previously been ground in a porcelain dish. A gel was formed after 26.5 ml of a 1 molar agueous ammonium hydroxide solution were added all at once.
Without support AS-Ds 127 The examples 45 to 48 below prove that the polymerized substance according to the invention is cros~linked via ester bonds and not only via hydrogen bonds.
' ,:
~xam~le 4 1 g of cationic potato starch, Caticnamyl 9852, AGENA, Austria, were made into a paste in 150.6 g of distilled water at 70C for 20 minutes and the mixture was treated with 0.5 g of NA/NV2 copolymer, prepared in Example 1, and dispersed in 9.S ml of distilled water, and the mixture was stirred for 30 seconds, after which 3.84 ml of a 1 molar aquQous sodium hydroxide solution were added all at once which resulted in the formation of a gel. The solids content of the reaction mixture (solids employed in g x 100) '', - , .. - , ........ .. . . . . . .- -. ..... . - . . :
,.
200Q4~8 total weight in g was 1 % in this case. After the reaction mixture had cooled to room temperature, the viscosity was determined.
5Reaction mixtures of solids contents of 2 % and 3 %
were prepared in the ~ame manner using the appropriate amount~ of starting substances.
For comparison, reaction mixtures having solids contents of 1, 2 and 3 % were prepared in the same manner 10but using a MA/MVE copolymer, prepared in Example 1, in which the acid anhydride groups were hydrolyzed complete-ly prior to addition to the reaction mixture by stirring in distilled water for 14 hours, and the viscosities of these reaction mixtures were determined. The degree of 15neutralization wa3 60 % in all c~ses, that is to say, 60 % of the acid groups in the polymerized substance were present in the form of the Na salt, and the pH was 7.5 The viscosity was determined with the aid of a Brookfield Viscometer, Synchro Lectric Viscometer, Model 20LVT. ~he following viscosities were measured: ;
. .
Solids content Viscosity in mPas - in per cent According to Compari~on the invention 1 520 120 -;
3 339000 21~0 ' .
~xa~le 46 2 g of polyvinyl alcohol, Mowiol 8-88, Hoechst, FRG, were dissolved in 89.1 g of distilled water at 80C, and the solution was treated with 1 g of MA/~YE copolymer, i -prepared in Example 1, and dispersed in 9 ml of water, and the mixture wa~ stirred for 30 seconds, after which 3.2 ml of a 1 molar aqueous sodium hydroxide solution were added all at once, which resulted in the formation of a gel. The solids content of the reaction mixture was 3 %. After the reaction mixture had cooled to room temperature, the viscosity was determined.
.
' ' .''''''~ ' I' '' . '': ' ' ~ ' " '' ' ' . ' :', . ' 200Q4~8 Reaction mixtures having solids contents of 5 % and 7 ~ were prepared in the same manner using the appro-priate amounts of starting substances, and the viscosities of these reaction mixtures were measured.
For comparison, reaction mixtures were prepared in the same manner, but u3ing a NA/MVE copolymer, prepared in Example 1, in which the acid anhydride groups were completely open prior to the addition to the reaction mixture by stirring in distilled water for 14 hours, and the viscosities of these reaction mixtures were deter-mined. The degree of neutralization was 25 % in all cases and the pH was 4.05.
Solids content Viscosity in mPas in per cent According to Comparison the invention - . . . : .- - : - . : . . :
example, steam and/or pressure treatment. To coat fibres, polymer A, polymer B and - all at once - the base can be incorporated into a suspension of fibres, so that the absorbing product i8 formed directly in the reaction mixture. Furthermore, it is possible to spray polymer A, polymer B and the base in solution or dispersion onto a continuously moving length of support. In this case, polymer A, polymer B and the base can be sprayed on either individually or together.
In a particularly preferred embodiment, an aqueous solution of polymer A is combined with polymer B
which is employed in the form of a powder in aqueou~
dispersion. This dispersion and the solution of the base, both of which are as concentrated as possible, are propelled through nozzles with the aid of pressurized air or steam and sprayed onto the support. In thi case, the base can be mixed with polymer A and polymer B either within the nozzle or outside the nozzle. If a length of paper i8 used as the support, and if the reaction mixture is applied in a highly concentrated form and only in small amounts, it is possible for in particular an over-dried paper to take up the entire moisture.
If the support contains free hydroxyl groups, such as, for example, in the case of cellulose-containing supports, the former can be involved in the crosslinking proce~s 80 that particularly good bonding to the support takes place when the absorbing layer is formed.
The absorbing products ha~e excellent absorption properties, the bonding between support and polymer ~
being good and durable, and they can be pre-pared Qasily, rapidly and with a low input of energy and costs, and therefore represent an enrichment of the art.
Exa~ple 1 Maleic anhydride/methyl vinyl ether (MA~NV~ copolymer) 87.3 g of maleic anhydride and 1.46 g of di-lauroyl peroxide were introduced into a 2 1 Juchheim pre~surized reaction vessel, and the reaction apparatus wa~ then flushed with nitrogen. When the apparatus was free from oxygen, 310 g of methyl vinyl ether which had '" ' . '. ' : . ... ' , '. ' . . `. ~.' ~ . ' : :
," ' , . ' ~: '''.' ' :' '.
. '" , '' ' . ' ' " " .~ ' ' , ': ' ~: ' ' ~ ' ~, ' , ' .
.. : '' ,: ' .
ZQOQ4~L8 been dried over solid sodium hydroxide and freshly di~tilled, were added. The react.Lon mixture was warmed to 55C with stirring and maintainecl at thi~ temperature for 2 hours under pressure. After the mixture had cooled to 20C, excess methyl vinyl ether was di~tilled off, and the reaction product was removed from the ves~el. Thi~
gave 118 g (84.9 % of theory) of an MA/MV~ copolymer having the following properties: loss on drying at 105C:
0.92 %, at 60C in vacuo: 0.25 %. The particle size 10 distribution~ which was measured by sieve analysi~, gave the following values:
Particle size (micrometers) (%) below 32 43.6 32 - 44 7.6 44 - 100 13.0 100 - 200 14.0 200 - 354 14.2 354 - S00 5.8 500 - 710 0.6 710 - 850 0.6 850 - 1400 0.6 Conditionss Alpine air-~et sieve, 0.02 bar vacuum;
sieving ti~e: 7 minutes. The specific vi~cosity was determined as followss 0.5 g of MA/NVE copolymer was ~ -dissolved in 50 ml of methyl ethyl ketone and the 801u-tion was stirred for 1 to 2 hours at roo~ temperature.
The specific viscosity was measured with the aid of a Ubbelohde viscometer and was 3.2.
The hydrolysis rate of the MA groups wa~ determined as follow~.
17.5 ml of a 0.1 molar aqueous sodium hydroxide solution and 76 ml of distilled wat~r (having a pH of 12.4) w~re dispersed with 0.2 g of MA/MV~ copolymer in a 250 ml round-bottomed flask equipped with a RPG stirrer (blade diamsters 5 cm) at 250 rpm. The pH drop in the measuring apparatus was determined with the aid of a glass elec-trode. The hydrolysis time is defined as the period in minutes which i8 required for the pH to drop from pH 12.4 to pH 10Ø The hydrolysis rate was 30 minute~.
,- .- ...... . . : ~ ~
- , - .~ ......................................... . :
.. . . .. . . .
~ ~0~ ~8 Example 2 Polymer A: Polyvinyl alcohol (PVAL), Mowiol 8-88, Hoechst, FR~
Polymer B: Maleic anhydride/methyl vinyl ether (MA/MVE) copolymer of Example I
100 g of 5 % by weight aqueous solution of polymer A were heated to 80C and treated with 5 g of polymer B in the form of a powder, with stirring. 30 ml of a 1 molar aqueous sodium hydroxide solution were then added all at once, which resulted in gel formation in the reaction vessel within one minute. The gel was brushed onto a plastic foil and dried at 100C. 0.17 mol ~ of the acid functions of polymer BL were pre~ent in the form of ester~. The absorption properties of the dried gel were determined in the following manner-The dried gel was scraped off the pla~tic foil.
About 0.2 g were transferred into a teabag and immersed in an aqueous test ~olution. The test solutions used were, on the one hand, di~tilled water, on the other hand a CIPAC-D standard solution which is an aqueous solution having an exactly defined ion content (CIPAC, Handbook, Vol. 1, Analysis of Technical Formulated Pesticides, R.
Ashworth, J. Henriet, J.F. Lovett, Cellaboration Inter-national Pesticide, Analytical Cou~cil, 1970, 875 to 879), and a 0.9 % by weight NaCl olution. After 24 hours, the teabag was re~oved from the test solution, placed on a filter paper base and turned without applica-tion of pressure until the e~cape of liquid had ceased (about 4 minutes). After this, the we~ght of the swelled ~ample was determined. The absorption capacity AC of the polymerized ~ub~tance for a test ~olution wa3 calculated as follows:
AC (g/g) = Weight of the swelled sample - weight of the dry polymer ;~
Weight of the dry polymer ,, , . . .. . - . , . --, - , .
- ,: . .. .
. . :
: . ~ .: - ' 2QOQ4~
AC-D is the absorption capacity for distilled water AC-C is the absorption capacity for a CIPAC-D standard solution AC-N is the absorption capacity of a 0.9 % by weight sodium chloride solution The gel had the following absorption propertie~:
AC-D: 434 AC-C: 49 AC-Ns 49 The same procedure was also used for determining the absorption capacitie~ of the absorbing polymer in the other examples.
Example 3 Polymer A: PVAL, ~owiol 4-88, Hoechst, FRG
Polymer B: NA/MVE copolymer of Example 1 ~ 27 % by weight aqueous solution of polymer A
was introduced in a mixing vessel at a flow of 7.4 g/min together with polymer B in the form of a powder, Ln an amount of 2 g/min, and the mixture was homogenized. The .
dispersion which formed was continuously withdrawn in an amount of 9.4 g/min, heated to 80C, mixed with 4 ml/min of a 17 % by weight aqueous sodium carbonate solution, immediately sprayed onto a paper length of width 23 c.m, moving at 12.4 m/min, and dried with hot air. To measure the absorption properties of the absorbing product, batches of 3 to 7 samples in the sh~pe of circles were punched out of the coated length of paper, immersed in test solutions as described in Example 1 and then treated as in ~xample 1. The absorption capacity of the absorb~ng product for a test solution was calculated as followR:
AC (g/g) Weight of the swelled sample - weight of the w~t support ; .;
Weight of the dry sample - weight of the dry support The absorbing product had the following absorp-. . ~: .......... .. - ........ - - :: . , :
: - ~ :... . . . . . - . .. .. . . .. .. . . .
2QOQ4~3 ~ 14 -tion properties:
AC-D: 244 AC-C: 41 The same procedure was used for determining the absorption capacity of the absorbing products in the other examples.
Example 4 Polymer A: PVAL, Mowiol 4-88, Hoechst, FRG
Polymer B: MA/MVE copolymer of E~ample 1 100 g of a 24.8 ~ by weight aqueous solution of polymer A were heated to 80C and treated with 24.8 g of polymer B in the form of a powder, with stirring. After this, 39.4 g of a 20 % by weight aqueous sodium carbonate isolution were added all at once. After about 30 iseconds, the reaction mixture started foaming, this resulting in the formation of a foamed product which was brushed on and dried at 10~C.
Without support On paper AC-D: 214 203 ~C-C: 30 19 AC-N: 34 -Exa,lnDle ~
Polymer A: PVAL, Mowiol 4-88, Hoechst, FRG
Polymer B: MA/NVE copolymer of Example 1 The procedure of Example 2 was followed, but at a reaction and drying temperature of 25C, this giving 2 dried gel having the following propertie~s . .
Without support On paper AC-Ds 142 191 AC-Cs 31 25 AC-N: 38 -O.084 mol % of the acid functions of polymer B were present in the form of an ester.
.. .. - ~
~, :
2QOQ4~8 Example 6 Polymer A: PVAL, Mowiol 8-88, Hoechst, FRG
Polymer B: MA~MVE copolymer of Example 1 50 g of a 10 % by weight solution of polymer A
were warmed to 80C and treatecl with 1 g of polymer B, with stirring. After this, 30 ml of a 1 molar aqueous ammonium hydrogen carbonate solution were added all at once, which made the reaction mixture foam, and a foamed product was formed.
Without support On paper AC-D: 393 140 AC-C: 36 12 AC-N: 33 Example 7 A~ d~scribed in Example 6, but using 30 ml of a O.5 molar, aqueous guanidine carbonate solution as the base, a gel being obtained.
On paper AC-C: 24 AC-~: 34 Example 8 - Polymer As Carboxymethylcellulose tCMC), Cekol-DVEP Type, Billerud, Sweden;
Polymer B: MA/MVE copolymer of Example 1 100 g of a 5 ~ by weight solution of polymer A
were heated to 80C and treated with S g of polymer B, with stirring. A gel was formed within one minute by adding 30 ml of a 1 molar aqueous sodium hydroxide solution all at once.
!
Without support On paper AC-D: 55 65 AC-C: 64 .:
: .. .. - . . .. : ,- ., . .:.. .: . .. .. - .: ~
., . , . . . . . .. . ., . . ... . - .
- -. ~ . . ,. ~ .. . . .- . .
2QOQ4~8 Example 9 Polymer A: Sodium alginate, Protanal LF 20J60, AMEA, Austria Polymer B: MA/MVE copolymer of ]~xample 1 4.5 g of polymer A and 4.5 g of polymer B were run into 145 ml of distilled water, and the mixture was then heated to 70C with stirring. A gel was formed in the course of 2 minutes by adding 28.8 ml of a 1 molar aqueou~ sodium hydroxide solution all at once.
Without support On paper AC-D: 208 214 AC-C: 72 68 Example 10 Polymer A: Hydroxypropyl starch, Solamyl 9570, AGENA, Austria Polymer Bs MA/MYE copolymer of Bxample 1 The procedure of Example 9 was followed, but using 160 ml of distilled water, 12 g of polymer A, 6 g of polymer B and 53.8 ml of a 1 molar aqueous sodiu~ :.
hydrox~de solution.
Without support On paper AC-Ds 220 180 AC-Cs 26 - :~
Example 11 Polymer As Cold-soluble starch, Sobex 242, Sudstarke, FRG
Polymer B: MA/NVE copolymer of Example 1 The procedure of Example 9 was followed, but using 160 ml of wa~er, 6 g of poly.mer A, 3 g of polymer B and 26.9 ml of a 1 molar, aqueous sodium hydroxide solution.
Without support On paper AC-Ds 227 123 Ar-cs- 20 : . , , 2QOQ4~.8 Example 12 Polymer A: Phosphate guar, Meyprofilm 500, Meyhsll, Switzerland Polymer ~: NS/MVE copolymer of Example 1 The procedure of Example 9 was followed, but using 160 ml of water, 6 g of polymer A, 6 g of polymer B and 38.4 ml of 1 molar aqueous sodium hydroxide solu-tion.
Without support On paper AC-D: 152 215 AC-C: 18 28 AC-N: 22 Example 13 Polymer A: Depolymerized guar, Meyprogat 90, Meyhall, Switzerland Polymer B; MA/MVE copolymer of Example 1 The procedure of Example 9 was followed, but usihg 160 ml of water, 3 g of polymer A, 3 g of polymer B
and 19.2 ml of a 1 molar aqueous sodium hydroxide solution.
Without support On paper AC-Cs 25 14 ~!~
AC-Ns 12 Example 14 Polymer As Native guar, Meyproguar CSA 200/50, ~eyh~
Switzerland Pol y r B: NA/MVE copolymer of Example 1 The proce~ure of Example 9 was followed, but using 160 ml of water, 3 g of polymer A, 3 g of po~ymar and 2 6 . 9 ml o f a 1 molar aqueou~ sodium hydroxide solution. :-.
Without support AC-D: 113 AC-C: 23 AC-N: 22 .
.
.
, .
Example 15 Polymer ~: Hydroxypropyl starch, Solamyl 9570, AGENA, Austria, and PVAL, Mowiol 4-88, Hoechst, FRG, in the ratio of 1:1 Polymer B: MA/MVE copolymer of Example 1 50 g of a 5 % by weight aqueous hydroxypropyl starch solution was made into a paste and treated at room temperature with 12.5 g of a 20 % by weight PVAL solu-tion, and the mixture was heated to 80C, after which 5 g of polymer B were added with stirring. A gel was formed within one minute after 30 ml of a 1 molar aqueous ~odium hydroxide solution were added all at once.
.
Without support On paper AC-D: 308 247 AC-C: 28 22 AC-N: 32 Example 16 Polymer A: Cold-soluble starch, Sobex 242, Sudstarke, FRG, and PVAL, Mowiol 4-88, Hoechst, FRG, in the ratio by weight of 1:1 Polymer Bs NA/MVE copolymer of ~xample 1 50 g of a 5 % by weight agueous starch solution were mixed with 12.5 g of a 20 % by weight aqueous PVAL
solution, and the mixture was heated to 80C and treated with 5 g of polymer B in the form of a powder. A gel was formed after 30 ml of a 1 molar aqueou~ potassium hydrox-ide solution were added all at once.
Without support On paper AC-D: 259 138 AC-C: 28 15 AC-Ns 27 Examp~e 17 Polymer As Sodium alginate, Protanal LF 20/60, AMEA, Austria, and PVAL, Mowiol 4-88, Hoechst, FRG
Polymer B: MA-MVE copolymer of Example 1 - . .
, ~ , .
.
X~Q~8 100 ml of a 3 % by weight aqueous sodium alginate solution and 7.5 g of a 20 % by weight aqueous PVAL
solution were mixed at room temperature, and the mixture was heated to 80C and treated with 4.5 g of polymer B in the form of a powder. A gel was formed after 27 ml of a 1 molar aqueous sodium hydroxide 501ution were added all at once.
Without support On paper AC-D: 250 220 AC-C: 67 52 Example 18 The procedure of Example 17 was followed, the ratio by weight of the ~tarting 3ubstances sodium alginate:PVAL:MA/MVE copolymer being 1:1:2.
15Without support On paper AC-D: 319 277 AC-C: 52 50 Example 19 ~ he procedure of Example 17 was followed, the ratio by weight of the starting substances sodium alginate:PYAL:MA/MVE copolymer be~ng 1:0.5:1.5.
Without support On paper AC-Ds 333 236 AC-C: 48 43 Examp~e 20 Polymer A: Carboxymethylcellulose (CMC), CEROL ~ :
HDEG,Billerud, Sweden, and :
PVAL, Mowiol 4-88, Hoechst, FRG
Polymer B: MA/NVE copolymer of Example 1 3080 g of a 4 % by weight aqueous solution of CMC
and 16 g of a 20 % by weight aqueous solution of PVAL
were heated to 82C and treated with 6.4 g of polymer B
in the form of a powder. A gel was formed within 1 minute i-`
'''"
.. . ... ~................ . . . ,- ~, ., , ~ . ..
2~0Q4~8 after 38.4 ml of a 1 molar aqueous sodium hydroxide solution were added all at once.
Without support On paper AC-D: 289 383 AC-C: 64 39 AC-N: 55 Ex~nple 21 Polymer A: Hydrolyzed wheat starch, Merigum C, Amylum, Belgium, and PVAL, Mowiol 8-88, Hoechst, FRG
Polymer B: MA/MVE copolymer of Example 1 6 g of wheat starch and 6 g of PVAL were made into a paste or dissolved, respectively, in 123 ml of distilled water at 82C, after which 6 g of MA~MVE co-polymer, dispersed in 20 ml of water, were added with stirring. A gel was formed within 30 to 50 seconds after 39 ml of a 1 molar aqueous sodium hydroxide 301ution were added all at once.
Without support On paper AC-Ds 374 188 AC-C~ 18 16 AC-Ns 18 Example 22 Polymer As Cationic potato starch, Cationamyl 9852, AGENA, Austria, and xanthan gum, Jungbunzlauer, Austria, Polymer Bs NA/MVE copolymer of Example 1 6 g of potato starch and 3 g of xanthan gum were made into a paste or dissolved, respectively, in 140 ml of distilled water at 80C, and treated with 3 g of polymer B which had been dispersed in 20 ml of water. A
gel was formed within 30 second~ after 27 ml of ~ 1 molar aqueous sodium hydroxide solution were added all at once.
. - . . .
- . ,:, . . ~ . . : .
2QQQ4~3 Without support On paper AC-D: 144 113 AC-C: 19 25 AC-N: 17 Examples 23 - 27 3 g of a range of comminuted cellulose materials were incorporated in 100 g of a 5 % by weight PVAL
solution (Mowiol 8-88, Hoech~t, FRG), and the mixture was stirred to form fine fibres. This mixture was heated to 80C and treated with 8 g of MA/MVE copolymer of Example 1. A gel was formed within 20 seconds after 48 ml of a 1 molar agueous sodium hydroxide solution were added all at once.
, Example 23 Cellulose material: Photocellulose, Borregaard, Austria PVALsCellulose:MA/MVE copolymer - 1:0.6:1.6 (5 g:3 g:8 gJ
48 ml of 1 molar NaOH ::
Without ~upport On paper AC-D: 334 254 AC-C: 24 23 AC-N: 18 ,:
Exa~ple 24 Cellulose material: Sulphatecellulo~e, degre~ of freene~s 12 SR, whitene~s 88.? %, P~ls, ~ -Austria .
PVAL:CellulosesMA/MYE copolymer = 1:0.6:1.6 (5 g:3 g:8 i 48 ml of 1 molar NaOH ~:-Without support On paper AC-D: 390 256 AC-C: 25 19 AC-N: 18 - :
. . . : . .- . . :. . - . .. . . . . . ~ . . . .. : . . . .. ~ . .
200Q4~3 Example 25 Cellulose material:tissue paper- A, Zewa, PWA, FRG
PVAL:Cellulose:NA/MVE copolymer = 1:0.6:1.6 (5 g:3 g:8 g) 48 ml of 1 molar NaOH
Without support On paper ~C-D: 284 251 AC-C: 29 27 AC-N: 22 Example 26 Cellulose material tissue paper B. Henry, Laakirchen, Austria PVAL:Cellulose:MA/MVE copolymer = 1:1:2 (5 g:5 g: 10 g) 60 ml of 1 molar NaOH
' Without support On paper AC-D: 227 196 AC-C: 23 28 AC-N: 23 Example 27 Cellulose material, sulphite cellulose, fully bleached, Steyrerm~hl, Au~tria PVAL:CellulosesMa copolymer = 1:1:2 (5 g:5 g:10 g) 60 ml of 1 molar NaOH
Without support On paper AC-D: 218 204 AC-C: 20 18 AS-N: 17 0.113 mol ~ of the acid functions of polymer B were preQent in the form of esters.
Example 28 PVAL succinate 100 g of a 36 % by weight aqueous PVAL solution (Mowiol 4-88, Hoechst, FRG) were stirred with 24.5 g of succinic anhydride and O.3 g of concentrated sulphuric .....
..
2al0Q4~8 acid for 1 hour at 60C. The reaction mixture was then cooled to room temperature and added dropwise to acetone, PVAL succinate being precipitated. The precipitate wa~
filtered off, washed with acetone and dried at 50C to constant weight. Thi~ gave 4g g of PVAL succinate. ~he degree of substitution DS wa determined titrimetrically.
The degree of substitution was 0.149 mol of succinic ester groups per mol of hydroxyl groups in the PVAL.
PVAL succinateq having degrees of substitution of 0.016; 0.038; 0.091 and 0.293 mol of ~uccinic ester groups per mol of hydroxyl groups in the PVAL were prepared following the above procedure u~ing appropriate amounts of succinic anhydride.
Compounds 29 to 33 were prepared following the procedure of Ex~mple 2 and using, in each case, 5 g of PVAL succinate of the appropriate degree of substitution DS, 5 g of polymer B and 30 ml of 1 molar aqueous sodium hydroxide solution: -Example 29 - 33 Polymer A: PVAL succinate of degree of substitution DS ~ ~i Polymer B: MA/NVE copolymer of Example 1 No.DS AC-D AC-C AC-N
withoutwithout without supportsupport support 290.016 431 54 50 300.038 398 6~ 52 310.091 353 64 48 320.149 400 64 41 330.293 424 61 43 Example 34 PVAL hydroxypropane~ulphonic acid ether 100 g of a 20 % by ~eight aqueous solution of PV~L, ~owiol 8-88, Hoechst, FRG, were treated with 17.8 g of a 25 % by weight aqueous ~olution of Na 3-chloro-2-hydroxypropanesulphonate (Na CHPS), and the mixture washeated to 60C. In this process, the pH was maintained at , ~, : , ~ . : ., : :
~QOQ~:18 8 by dropwise addition of a 20 % by weight aqueous sodium hydroxide solution. When the reaction was complete, the reaction solution was added dropwise to acetone, PVAL
hydroxypropanesulphonic acid ether being precipitated.
The precipitate was filtered ffr washed with acetone and dried. This gave 21 g of PVAL hydroxypropanesulphonic acid ether. PVAL hydroxypropanesulphonic acid ethers wer~ prepared following the above procedure using ap-propriate amounts of 3-chloro-2-hydroxypropanesulphonic acid ether.
The following polymerized sub3tances were pre-pared following the procedure described in Example 2 using 120 ml of a 1 molar aqueous sodium hydroxide solution, in each case 20 g of P~AL hydroxypropane-sulphonic acid e~her as polymer A, dissolved in 80 ml of distilled water, and in each case 20 g of MA/NVE copoly-mer as polymer B, prepared in ~xample 1:
Examples 35 - 39 No. Amount of AC-D On AC-C On AC-N
NaCHPS (25 % without paper without paper without b.w.) in g support support support 35 3.57 423 347 37 36 34 36 17.84 462 293 47 30 50 37 39.59 326 245 28 20 28 38107.08 268 398 34 24 43 39278.48 337 358 34 26 35 Example 40 PVAL 2-hydroxypropane-3-(trimethylammonium chloride) ether 0.40 g of glycidyltrimethylammonium chloride were stirred into 200 ml of a 5 % by weight aqueous solution of PVAL, Mowiol 8-88, Hoechst, FRG, o~ Example 1 at room temperature, and the reaction mixture was heated to 60C
and maintained at pH 8 by continuous addition of an aqueous sodium hydroxide solution. After 2 hours, the reaction mixture was cooled to room temperature, and the . . . : . : . .: ~ ., , - , ~ , . . . . . .
~ , - . . - .
2QOQ41~3 , product formed wa~ precipitated by adding acetone, filtered off, washed and dried at 50C. This proces~ gave 10.4 g of the title compound.
Example 41 A product having the following properties was obtained following the procedure described in Example 2 and using 5 g of the product of Example 40, di~solved in 100 ml of distilled water, 5 g of MA/NVE copolymer prepared in Example 1 in the form of a powder and 30 ml 10 of a 1 molar aqueou~ sodium hydroxide solution:
Without support AC-D: 3s3 AC-C: 35 AC-N: 51 :
Exam~le 42 6 g of cationic potato starch (Amylofax 15, DS = 0.027, AVE8E, NL) and 6 g of PVAL (Mowiol 8-88, Hoechst, FRG) were made into a paste, or dissolved, respectively, in 123 ml of water at 82C, and the mixture was treated with 6 g of MA/MV~ copolymer, prepared in Example 1, ~nd di~persed in 20 ml of water. A gel was formed within ~econds after 39 ml of 1 molar aquaous sodium hydroxide solution were added all at once.
Without support On paper AC-Ds 253 159 :
AC-C: 18 16 AC-Ns 16 - .
Example 43 -~
6 g of cationic potato starch (Amylofax 15, DS = 0.027, AYEBE, NL) and 3 g of CMC (CEROL HDEG, :
Billerud, Sweden), were made into a paste, or dissolved, respectively, in 140 ml of distilled water at 80C, and the mixture was treated with an aqueous di~persion of 3 g of MA/MVE copolymer, prepared in Example 1, in 20 ml of `
.. ..
, : .: , . . ; . .
ZOOQ4~L8 water. A gel was formed within a few seconds after 27 ml of 1 molar aqueous sodium hydroxide ~olution were added all at once.
; Without support On paper AC-D: 230 156 AC-C: 32 30 ! Example 44 Polymer A: Cationic potato starch, Cationamyl 9852, AGENA, Austria Polymer B: MA/isobutylene copolymer, Isobam-10, Ruraray, Japan 6 g of polymer A were mada into a paste in 160 ml of distilled water at 70C, and the mixture was treated with stirring with 3 g of polymer B which had previously been ground in a porcelain dish. A gel was formed after 26.5 ml of a 1 molar agueous ammonium hydroxide solution were added all at once.
Without support AS-Ds 127 The examples 45 to 48 below prove that the polymerized substance according to the invention is cros~linked via ester bonds and not only via hydrogen bonds.
' ,:
~xam~le 4 1 g of cationic potato starch, Caticnamyl 9852, AGENA, Austria, were made into a paste in 150.6 g of distilled water at 70C for 20 minutes and the mixture was treated with 0.5 g of NA/NV2 copolymer, prepared in Example 1, and dispersed in 9.S ml of distilled water, and the mixture was stirred for 30 seconds, after which 3.84 ml of a 1 molar aquQous sodium hydroxide solution were added all at once which resulted in the formation of a gel. The solids content of the reaction mixture (solids employed in g x 100) '', - , .. - , ........ .. . . . . . .- -. ..... . - . . :
,.
200Q4~8 total weight in g was 1 % in this case. After the reaction mixture had cooled to room temperature, the viscosity was determined.
5Reaction mixtures of solids contents of 2 % and 3 %
were prepared in the ~ame manner using the appropriate amount~ of starting substances.
For comparison, reaction mixtures having solids contents of 1, 2 and 3 % were prepared in the same manner 10but using a MA/MVE copolymer, prepared in Example 1, in which the acid anhydride groups were hydrolyzed complete-ly prior to addition to the reaction mixture by stirring in distilled water for 14 hours, and the viscosities of these reaction mixtures were determined. The degree of 15neutralization wa3 60 % in all c~ses, that is to say, 60 % of the acid groups in the polymerized substance were present in the form of the Na salt, and the pH was 7.5 The viscosity was determined with the aid of a Brookfield Viscometer, Synchro Lectric Viscometer, Model 20LVT. ~he following viscosities were measured: ;
. .
Solids content Viscosity in mPas - in per cent According to Compari~on the invention 1 520 120 -;
3 339000 21~0 ' .
~xa~le 46 2 g of polyvinyl alcohol, Mowiol 8-88, Hoechst, FRG, were dissolved in 89.1 g of distilled water at 80C, and the solution was treated with 1 g of MA/~YE copolymer, i -prepared in Example 1, and dispersed in 9 ml of water, and the mixture wa~ stirred for 30 seconds, after which 3.2 ml of a 1 molar aqueous sodium hydroxide solution were added all at once, which resulted in the formation of a gel. The solids content of the reaction mixture was 3 %. After the reaction mixture had cooled to room temperature, the viscosity was determined.
.
' ' .''''''~ ' I' '' . '': ' ' ~ ' " '' ' ' . ' :', . ' 200Q4~8 Reaction mixtures having solids contents of 5 % and 7 ~ were prepared in the same manner using the appro-priate amounts of starting substances, and the viscosities of these reaction mixtures were measured.
For comparison, reaction mixtures were prepared in the same manner, but u3ing a NA/MVE copolymer, prepared in Example 1, in which the acid anhydride groups were completely open prior to the addition to the reaction mixture by stirring in distilled water for 14 hours, and the viscosities of these reaction mixtures were deter-mined. The degree of neutralization was 25 % in all cases and the pH was 4.05.
Solids content Viscosity in mPas in per cent According to Comparison the invention - . . . : .- - : - . : . . :
Claims (10)
1. Absorbing polymer consisting of a polymer A and a polymer B, comprising polymer A being resent in an amount of 10 to 99 percent by weight and being an optionally modified polyvinyl alcohol or an optionally modified polysaccharide or a mixture of these, and polymer B being present in an amount of 1 to 90 percent by weight and being a maleic anhydride homo- or copolymer having a hydrolysis time of 5 to 120 minutes, the anhydride groups being opened and 0.005 to 5 % of the acid functions in polymer B being esterified with hy-droxyl groups of polymer A and the remaining acid func-tions being present as free acid groups, as salts or as acid amide groups.
2. Absorbing polymer according to Claim 1, comprising polymer A being a modified polyvinyl alcohol.
3. Absorbing polymer according to Claim 1, comprising polymer A being carboxymethylcellulose.
4. Absorbing polymer according to Claim 1, comprising polymer B being a maleic anhydride/methyl vinyl ether copolymer.
5. Absorbing polymer according to Claims 1, comprising the hydrolysis time of polymer B being 10 to 60 minutes.
6. Absorbing polymer according to Claims 1, comprising polymer A being present in an amount of 40 to 95 per cent by weight and polymer B in an amount of 5 to 6 per cent by weight.
7. Process for the preparation of an absorbing polymer comprising combining an option-ally modified polyvinyl alcohol, an optionally modified polysaccharide or mixtures of these with a maleic anhydride homo-or copolymer having a hydrolysis time of 5 to 120 minutes, and the mixture treated at a temperature of 20 to 120°C with 0.5 to 1.6 equivalents, added all at once, of an inorganic or organic base per equivalent of maleic anhydride.
8. Absorbing product, comprising the absorbing polymer according to Claim 1 being bonded to one or more supports.
9. Absorbing product according to Claim 8, comprising the support or supports being one or more lengths of paper.
10. Process for the preparation of an absorbing product according to Claim 8, comprising applying a polymer A, a polymer B and an aqueous solution of an inorganic or organic base to and/or between one or more supports, if appropriate with heating, and drying.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0255988A ATA255988A (en) | 1988-10-14 | 1988-10-14 | ABSORBENT POLYMER |
| ATA2559/88 | 1988-10-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2000418A1 true CA2000418A1 (en) | 1990-04-14 |
Family
ID=3536445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002000418A Abandoned CA2000418A1 (en) | 1988-10-14 | 1989-10-11 | Absorbing polymer |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4990551A (en) |
| EP (1) | EP0366968A1 (en) |
| AT (1) | ATA255988A (en) |
| CA (1) | CA2000418A1 (en) |
| DE (1) | DE3837535A1 (en) |
| FI (1) | FI894848A0 (en) |
| NO (1) | NO894027L (en) |
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|---|---|---|---|---|
| US5162430A (en) * | 1988-11-21 | 1992-11-10 | Collagen Corporation | Collagen-polymer conjugates |
| US5364792A (en) * | 1989-02-02 | 1994-11-15 | Hybrivet Systems, Inc. | Test swab and method of making and using same |
| US5330917A (en) * | 1989-02-02 | 1994-07-19 | Hybrivet Systems, Inc. | Test swab device and method of detecting lead, mercury, arsenic, and bismuth |
| US5550061A (en) * | 1989-02-02 | 1996-08-27 | Hybrivet Systems, Inc. | Test swab and method of using same |
| DE4029593C2 (en) * | 1990-09-19 | 1994-07-07 | Stockhausen Chem Fab Gmbh | Process for the preparation of absorbent material based on polymer with improved degradability and absorption of water, aqueous solutions and body fluids and the use in hygiene articles and for soil improvement |
| DE4029592C2 (en) * | 1990-09-19 | 1994-07-14 | Stockhausen Chem Fab Gmbh | Polymer-based swelling agents and absorbents with improved degradability and absorption of water, aqueous solutions and body fluids, and their use for the production of hygiene articles and for soil improvement |
| US5247072A (en) * | 1991-10-25 | 1993-09-21 | Kimberly-Clark Corporation | Carboxyalkyl polysaccharides having improved absorbent properties and process for the preparation thereof |
| US5550189A (en) * | 1992-04-17 | 1996-08-27 | Kimberly-Clark Corporation | Modified polysaccharides having improved absorbent properties and process for the preparation thereof |
| US5998032A (en) | 1992-08-17 | 1999-12-07 | Weyerhaeuser Company | Method and compositions for enhancing blood absorbence by superabsorbent materials |
| US6340411B1 (en) | 1992-08-17 | 2002-01-22 | Weyerhaeuser Company | Fibrous product containing densifying agent |
| ES2182830T3 (en) | 1992-08-17 | 2003-03-16 | Weyerhaeuser Co | METHOD OF UNION OF PARTICLES TO FIBERS. |
| JP3274550B2 (en) * | 1993-08-03 | 2002-04-15 | 株式会社日本触媒 | Manufacturing method of water absorbing material |
| US5739005A (en) * | 1995-03-17 | 1998-04-14 | Auburn University A Public University Of The State Of Alabama | Use of polymeric films for delivery of nematode eggs and ecological evaluations |
| GB2343962A (en) * | 1998-10-13 | 2000-05-24 | Datasorb Limited | Liquid absorption and weighing |
| US6899958B2 (en) * | 2002-06-21 | 2005-05-31 | Encap Technologies, Llc. | Moisture barrier resins |
| US20040058605A1 (en) * | 2002-09-19 | 2004-03-25 | Hansen Michael R. | Polysaccharide treated cellulose fibers |
| US20050000669A1 (en) * | 2003-03-14 | 2005-01-06 | Hugh West | Saccharide treated cellulose pulp sheets |
| US20050031841A1 (en) * | 2003-08-05 | 2005-02-10 | Weyerhaeuser Company | Attachment of superabsorbent materials to fibers using oil |
| US20050133180A1 (en) * | 2003-12-19 | 2005-06-23 | Hugh West | Densification agent and oil treated cellulose fibers |
| US20050178518A1 (en) * | 2004-02-13 | 2005-08-18 | Hugh West | Sodium sulfate treated pulp |
| MY178465A (en) * | 2008-01-04 | 2020-10-14 | Unilever Plc | Hand washing assessment method |
| CN107903410B (en) * | 2017-11-28 | 2020-09-25 | 嘉兴普元新材料科技有限公司 | Isobutene-maleic anhydride alternating copolymer/sodium alginate hydrogel and preparation method thereof |
| CN107973942B (en) * | 2017-11-28 | 2020-09-25 | 嘉兴普元新材料科技有限公司 | Isobutene-maleic anhydride alternating copolymer/sodium alginate hydrogel and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE478127C (en) * | 1924-01-31 | 1929-06-22 | I G Farbenindustrie Akt Ges | Process for the production of polysaccharide esters of high molecular weight, polyunsaturated fatty acids |
| DE1174753B (en) * | 1962-02-07 | 1964-07-30 | Gevaert Photo Prod Nv | Process for the preparation of polysaccharide carboxylic acid esters |
| GB1145961A (en) * | 1966-01-07 | 1969-03-19 | Monsanto Chemicals | Resin process |
| FR2109103A5 (en) * | 1970-10-01 | 1972-05-26 | Rhone Poulenc Sa | Vinyl alcohol copolymer derivs - prepd from saponified terpolymer contg ion exchange gps |
| CA972707A (en) * | 1971-06-11 | 1975-08-12 | Union Carbide Corporation | Process for cocrosslinking water soluble polymers and products thereof |
| US3941730A (en) * | 1972-06-05 | 1976-03-02 | E. I. Du Pont De Nemours And Company | Polyvinyl alcohol microgel precursor blends |
| DE2357079C2 (en) * | 1973-11-15 | 1982-07-29 | Hoechst Ag, 6000 Frankfurt | Process for the production of cellulose ethers which absorb water but are more than 50% insoluble therein |
| US4200557A (en) * | 1973-12-07 | 1980-04-29 | Personal Products Company | Absorbent product including grafted insolubilized cellulose ether |
| GB1508123A (en) * | 1973-12-19 | 1978-04-19 | Unilever Ltd | Process for preparing carboxyalkylated starch derivatives |
| JPS54125896A (en) * | 1978-03-23 | 1979-09-29 | Kuraray Co | Absorbing body that have excellent water absorbing capacity |
| US4169818A (en) * | 1978-04-17 | 1979-10-02 | Celanese Corporation | Mixture of hydroxypropylcellulose and poly(maleic anhydride/alkyl vinyl ether) as a hydrocolloid gelling agent |
| RO76052A (en) * | 1978-05-31 | 1981-11-04 | Hoechst Ag,De | PROCESS AND INSTALLATION FOR CARBOHYCELLYL-CELLULOSE CELLULOSE AND GOMFLABLE |
| NL7908799A (en) * | 1978-12-22 | 1980-06-24 | Tno | PROCESS FOR PREPARING A POLYMER MIX, PRODUCTS PRODUCED THEREFROM AND POLYMER ALLOY. |
| DE2900110A1 (en) * | 1979-01-03 | 1980-07-10 | Wolff Walsrode Ag | SOLUBLE MACROMOLECULAR SUBSTANCES WITH HIGH DISPERSION, SUSPENDING AND LIQUID RETENTION RESISTANCE, METHOD FOR THEIR PRODUCTION AND USE |
| GB2046774B (en) * | 1979-03-21 | 1983-08-03 | Advance Tapes Uk Ltd | Articles of manufacture having adhesive properties |
| GB2046773B (en) * | 1979-03-21 | 1983-08-03 | Advance Tapes Uk Ltd | Gelatinous articles and compositions |
| JPS55146786A (en) * | 1979-05-02 | 1980-11-15 | Fuji Photo Film Co Ltd | Ink-jet recording sheet |
| DE2923435A1 (en) * | 1979-06-09 | 1980-12-11 | Hoechst Ag | METHOD FOR THE PRODUCTION OF SWELLABLE, CROSSLINKED ETHERS OF POLYVINYL ALCOHOL AND THE USE THEREOF |
| US4381320A (en) * | 1981-06-03 | 1983-04-26 | Johnson & Johnson | Non-ionic absorbent polymers |
| DD212969A1 (en) * | 1982-12-30 | 1984-08-29 | Adw Inst Polymerenchemie | PROCESS FOR MODIFYING CARBOXYMETHYL CELLULOSE |
| US4511682A (en) * | 1983-06-28 | 1985-04-16 | Union Carbide Corporation | Water-dispersible coating compositions and process |
| US4575532A (en) * | 1984-02-08 | 1986-03-11 | Norchem, Inc. | Polyvinyl alcohol alloys and method of making the same |
| US4657537A (en) * | 1985-05-15 | 1987-04-14 | The Procter & Gamble Company | Disposable absorbent articles |
| US4743244A (en) * | 1985-06-28 | 1988-05-10 | Arco Chemical Company | Water absorbing polymer compositions and articles prepared therefrom |
| DE3634956A1 (en) * | 1986-10-14 | 1988-04-21 | Huels Chemische Werke Ag | METHOD FOR PRODUCING POLYMAL ACID ANHYDRIDE POWDER |
| CA1286465C (en) * | 1986-11-20 | 1991-07-23 | Adrian Swinburn Allen | Absorbent polymeric materials and their manufacture |
| JP2613604B2 (en) * | 1986-11-20 | 1997-05-28 | アライド・コロイズ・リミテツド | Absorbable products |
| US4788237A (en) * | 1986-12-15 | 1988-11-29 | Arco Chemical Company | Sugar-containing water-absorbing composition which facilitates fiber formation |
-
1988
- 1988-10-14 AT AT0255988A patent/ATA255988A/en not_active Application Discontinuation
- 1988-11-04 DE DE3837535A patent/DE3837535A1/en not_active Withdrawn
-
1989
- 1989-10-05 EP EP89118455A patent/EP0366968A1/en not_active Ceased
- 1989-10-09 NO NO89894027A patent/NO894027L/en unknown
- 1989-10-11 CA CA002000418A patent/CA2000418A1/en not_active Abandoned
- 1989-10-13 US US07/427,683 patent/US4990551A/en not_active Expired - Fee Related
- 1989-10-13 FI FI894848A patent/FI894848A0/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0366968A1 (en) | 1990-05-09 |
| US4990551A (en) | 1991-02-05 |
| NO894027D0 (en) | 1989-10-09 |
| DE3837535A1 (en) | 1990-05-10 |
| NO894027L (en) | 1990-04-17 |
| ATA255988A (en) | 1993-05-15 |
| FI894848A0 (en) | 1989-10-13 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |