SE428211C - A PARTICULATED ABSORPTION MATERIAL BASED ON A NITRIL IMPOLYMER AND A CROSS-BONDED CARBOHYDRATE POLYMER AND PROCEDURE FOR PREPARING IT - Google Patents
A PARTICULATED ABSORPTION MATERIAL BASED ON A NITRIL IMPOLYMER AND A CROSS-BONDED CARBOHYDRATE POLYMER AND PROCEDURE FOR PREPARING ITInfo
- Publication number
- SE428211C SE428211C SE7900528A SE7900528A SE428211C SE 428211 C SE428211 C SE 428211C SE 7900528 A SE7900528 A SE 7900528A SE 7900528 A SE7900528 A SE 7900528A SE 428211 C SE428211 C SE 428211C
- Authority
- SE
- Sweden
- Prior art keywords
- absorbent material
- carbohydrate polymer
- acrylonitrile
- crosslinked
- methacrylonitrile
- Prior art date
Links
- 229920001282 polysaccharide Polymers 0.000 title claims description 23
- 239000000463 material Substances 0.000 title claims description 20
- 238000010521 absorption reaction Methods 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 4
- 230000002745 absorbent Effects 0.000 claims description 15
- 239000002250 absorbent Substances 0.000 claims description 15
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 14
- 238000007127 saponification reaction Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 9
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 8
- 229920000578 graft copolymer Polymers 0.000 claims description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 229920002472 Starch Polymers 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 5
- 230000001588 bifunctional effect Effects 0.000 claims description 4
- 229920002307 Dextran Polymers 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000003756 stirring Methods 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 239000001341 hydroxy propyl starch Substances 0.000 description 2
- 235000013828 hydroxypropyl starch Nutrition 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 206010021639 Incontinence Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002825 nitriles Chemical group 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
7900528-6 ~ 2 'och 4.045.387 har synnerligen gbd absorptionsförmåga för vatten- haltiga vätskor, men absorptionshastigheten är för många använd- ningsområden alltför låg. Detta gäller speciellt i samband med användning i barnblöjor och dambindor. Det föreligger alltså ett stort behov av ett absorptionsmaterial som både har tillfredsställande absorptionsförmåga och hög absorptions- hastighet. 7900528-6 ~ 2 'and 4,045,387 have extremely gbd absorbency for aqueous liquids, but the absorption rate is too low for many applications. This is especially true in connection with use in baby diapers and sanitary napkins. There is thus a great need for an absorption material which has both a satisfactory absorption capacity and a high absorption rate.
Man har nu enligt föreliggande Uppfinning helt ÖVeffaSkande7 kunnat tillfredsställa nämnda behov och åstadkommit ett partiku- lärt absorptionsmaterial innefattande en vattenolöslig karboxyl- qruppsinnehållande förtvålningsprodukt av en ymppolymer av akrylnitril eller metakrylnitril och en kolhydratpolymer, vilket absorptionsmaterial har en hög absorptionsförmåga i kombination med en förbättrad absorptionshastighet avseende vattenhaltiga vätskor. Absorptionsmaterialet kännetecknas av att kolhydrat- polymeren utgöres av tvärbunden stärkelse, cellulosa; dextran eller ett derivat därav, varvid tvärbindningen åstadkommits med hjälp av ett bifunktionellt ämne, till exempel epiklorhydrin och att molförhållandet av tvärbunden kolhydratpolymer till akrylnitril eller metakrylnitril är l : l - l : 10.It has now been possible according to the present invention to completely satisfy said need and to provide a particulate absorbent material comprising a water-insoluble carboxyl group-containing saponification product of a graft polymer of acrylonitrile or methacrylonitrile and a carbohydrate polymer having an absorption capacity aqueous liquids. The absorbent material is characterized in that the carbohydrate polymer consists of crosslinked starch, cellulose; dextran or a derivative thereof, the crosslinking being effected by means of a bifunctional substance, for example epichlorohydrin, and the molar ratio of crosslinked carbohydrate polymer to acrylonitrile or methacrylonitrile being 1: 1 to 1: 10.
'Som_eXempe1 på lämpliga derivat av sådana polymerer kan nämnas hydroxypropylstärkelse, hydroxyetylcellulosa och karboxymetvl- dextran.Examples of suitable derivatives of such polymers are hydroxypropyl starch, hydroxyethylcellulose and carboxymethyldextran.
Tvärbindningsn av kolhydratpolymeren åstadkommas enligt ovan med hjälp av ett bifunktionellt ämne såsom epiklorhydrin. Sådana tvärbundna kolhvdratpolymerer med eller utan anjoniska och katjoniska grupperär i och för sig förut beskrivna bl.a. i de svenska patenten 169.293, 209.018, 222.291 och 358.894.The crosslinking of the carbohydrate polymer is accomplished as above by means of a bifunctional substance such as epichlorohydrin. Such crosslinked carbohydrate polymers with or without anionic and cationic groups are per se previously described i.a. in the Swedish patents 169,293, 209,018, 222,291 and 358,894.
Dessa tvärbundna kolhydratpolymerer bildar ett tredimensionellt nätverk, sammanhållet av kovalenta bindningar. De är olösliga i vatten, men har förmåga att svälla i vattenhaltiga vätskor _under bildning av en gel. Sådana tvärbundna kolhydratpolymerer har gelkromatografiska egenskaper.These crosslinked carbohydrate polymers form a three-dimensional network, held together by covalent bonds. They are insoluble in water, but have the ability to swell in aqueous liquids, forming a gel. Such crosslinked carbohydrate polymers have gel chromatographic properties.
Den tvärbundna kolhydratpolymeren skall ha en bäddvolym som överstiger lÛ ml/g, företrädesvis 15 ml/g. 7900528-6 Bäddvnlymon ör den volym som 1 grnm korr tvärbunden kolhydrat- polymer intar efter fullständig svällning i destillerat vatten.The crosslinked carbohydrate polymer should have a bed volume in excess of 10 ml / g, preferably 15 ml / g. 7900528-6 Bed lymon is the volume that 1 gram of cross-linked carbohydrate polymer occupies after complete swelling in distilled water.
Ymppolymerisationen mellan akrylnitril eller metakrylnitril och den tvärbundna kolhydratpolymeren utföres analogt med de metoder som används för ymppolymerisation av akrylnitril och stärkelse enligt de amerikanska patenten 3.997.484 och 4.045.387.The graft polymerization between acrylonitrile or methacrylonitrile and the crosslinked carbohydrate polymer is carried out analogously to the methods used for graft polymerization of acrylonitrile and starch according to U.S. Patents 3,997,484 and 4,045,387.
Förtvålningen omvandlar enligt kända principer nitrilsubstitu- enterna i ymppolymeren till karboxamid- och karboxylgrupper.According to known principles, the saponification converts the nitrile substituents in the graft polymer into carboxamide and carboxyl groups.
Halten av karboxylgrupper härrörande från förtvålningen skall vara sådan att jonbytarkapaciteten för dessa karboxylgrupper överstiger 1,5 mekv/g, företrädesvis 2,0 mekv/g.The content of carboxyl groups resulting from the saponification should be such that the ion exchange capacity of these carboxyl groups exceeds 1.5 meq / g, preferably 2.0 meq / g.
Kolhydratpolymeren eller ymppolymeren kan även bringas att 'innehålla anjoniska eller katjoniska grupper genom substitutions- reaktioner. De anjoniska och katjoniska grupperna kan anbringas på kolhydratpolymeren före eller efter tvärbindningen eller på ymppolymeren enligt kända förfaranden, exempelvis enligt svenska patentet 204.906. Karboxylgrupper och andra anjoniska grupper kan föreligga i syraform eller i form av exempelvis zink- eller alkalimetallsalter. lörtvålningen av ymppolymeren mellan akrylnitril eller metakryl- nitril och den tvärbundna kolhydratpolymeren utföres lämpligen med en alkalimetallhydroxid, exempelvis natriumhydroxid- För- tvålningen utföres vid en temperatur av 75-1300 C, företrädes- vis 75-1oo° c. ' l gram torrt absorptionsmaterial enligt uppfinningen kan absor- bera minst 20 ml vatten på 25 sek. 0fta kan emellertid nämnda mängd av materialet absorbera 20 ml vatten på 10 sekunder.The carbohydrate polymer or graft polymer may also be caused to contain anionic or cationic groups by substitution reactions. The anionic and cationic groups can be applied to the carbohydrate polymer before or after the crosslinking or to the graft polymer according to known methods, for example according to Swedish patent 204,906. Carboxyl groups and other anionic groups may be in acid form or in the form of, for example, zinc or alkali metal salts. The saponification of the graft polymer between acrylonitrile or methacrylonitrile and the crosslinked carbohydrate polymer is suitably carried out with an alkali metal hydroxide, for example sodium hydroxide. The saponification is carried out at a temperature of 75 DEG-130 DEG C., preferably 75 DEG-100 DEG C. the invention can absorb at least 20 ml of water in 25 seconds. However, said amount of the material can absorb 20 ml of water in 10 seconds.
Absorptionsmaterialet kan användas som sådant. Det kan emeller- tid också vara anbringat på eller inneslutet i en bärare av cellulosa, bomull eller dylikt.The absorbent material can be used as such. However, it can also be applied to or enclosed in a carrier of cellulose, cotton or the like.
Absorptionsmaterialet har genom sin goda absorptionsförmåga och förbättrade absorptionshastighet visat sig synnerligen -användbart i exempelvis barnblöjor. dambindor, inkontinenspåsar 'och liknande produkter. 79ÛÛ528'ë g 4 'Många andra tillämpningar är emellertid också tänkbara.Due to its good absorbency and improved absorption rate, the absorbent material has proven to be extremely useful in, for example, baby diapers. sanitary napkins, incontinence bags' and similar products. 79ÛÛ528'ë g 4 'However, many other applications are also conceivable.
Absorptionsmaterialet enligt uppfinningen bibehåller sin par- tikulära form även efter absorption av en vattenhaltig vätska.The absorbent material according to the invention retains its particulate shape even after absorption of an aqueous liquid.
Den absorberade vätskan kvarhålles dessutom effektivt i absorp- _tionsmaterialet. Någon vätska avges således inte till omgiv- ningen efter absorptionen.In addition, the absorbed liquid is effectively retained in the absorbent material. Thus, no liquid is released to the environment after absorption.
Absorptionsmaterialen enligt de amearikanska patenten 3.997.484 och 4.045.387 blir däremot slemmiga vid absorptionen av vatten- haltig vätska.The absorbent materials according to U.S. Patents 3,997,484 and 4,045,387, on the other hand, become slimy upon the absorption of aqueous liquid.
Kvätskan kvarhålles heller inte på ett tillfredsställande sätt i absorptíonsmaterialet, utan avges delvis till omgivningen, *exempelvis huden.The liquid is also not retained in a satisfactory manner in the absorption material, but is released partly to the environment, * for example the skin.
KUppfinningen förklaras närmare i anslutning till nedanstående utföringsexempel som visar framställning av olika absorptions- material enligt uppfinningen. I slutet av exempel l visas dessutom en jämförelse av absorptionsegenskaperna hos ett I I ' absorptionsmaterial enligt upp- finningen och två kända produkter.The invention is explained in more detail in connection with the following exemplary embodiments which show the production of various absorbent materials according to the invention. The end of Example 1 also shows a comparison of the absorption properties of an absorbent material according to the invention and two known products.
Exempel l ÉSD g kommersiell dextrin löstes i 500 ml 2 N natronlut inne- hållande 4 g natriumborhydrid. Den så erhållna lösningen fördes 'ner i en annan lösning bestående av Ü50 ml toluen och 9 g sta- bilísator GAC PE-510, GAF Corporation, Chemical >Division, New York, USA.* Blandningen värmdes till-600 C under omröring uvh försattes med 5ü ml epíklorhydrín. Därefter fortsatte reaktionen under omröring i 12 timmar vid 600 C.Example 1 ÉSD g of commercial dextrin was dissolved in 500 ml of 2 N sodium hydroxide solution containing 4 g of sodium borohydride. The solution thus obtained was poured into another solution consisting of 50 ml of toluene and 9 g of stabilizer GAC PE-510, GAF Corporation, Chemical Division, New York, USA. * The mixture was heated to 600 DEG C. with stirring and added. with 5ü ml epichlorohydrin. Thereafter, the reaction was continued with stirring for 12 hours at 600 ° C.
Reaktionsblandningen kyldes till 200 C och toluenet avskíldes i sugtratt. Den erhållna produkten tvättades med vatten, neu- traliserades och tvättades i destillerat vatten samt krymptes slutligen i etanol. Produkten torkades i torkskåp vid 700 C i 20 timmar. Man erhöll därvid 502 g produkt med bäddvolymen 18,0 ml/g) _ . ._ _ .__.-., ...... __... . ..._....._........._...___.._.. 5 7900528-6 86 g av produkten enligt ovan försattes med 1092 g destillerat vatten och värmdes till 300 C under omröring. Den så erhållna suspensionen försattes i tur och ordning med B0 g akrylnitril och 4,0 g cerium-ammoniumnitrat löst i 44 g 0,1 N salpetersyra.The reaction mixture was cooled to 200 DEG C. and the toluene was separated in a suction funnel. The resulting product was washed with water, neutralized and washed in distilled water and finally shrunk in ethanol. The product was dried in a drying cabinet at 700 ° C for 20 hours. 502 g of product with a bed volume of 18.0 ml / g) were obtained. ._ _ .__.-., ...... __.... ..._....._........._...___.._ .. 5 7900528-6 86 g of the product as above were added with 1092 g of distilled water and heated to 300 ° C while stirring. The suspension thus obtained was successively added with B0 g of acrylonitrile and 4.0 g of cerium ammonium nitrate dissolved in 44 g of 0.1 N nitric acid.
Reaktionen fick ske i 3 timmar under omröring. Termostate- ringen var hela tiden inställd på 300 C, men reaktionsbland- ningen antog 30 minuter efter satsningen av akrylnitril en temperatur av 550 C.The reaction was allowed to proceed for 3 hours with stirring. The thermostat was constantly set at 300 ° C, but the reaction mixture assumed a temperature of 550 ° C 30 minutes after the application of acrylonitrile.
Reaktionsblandníngen försattes med en lösning bestående av 50 g natriumhydroxid och 225 g vatten för åstadkommande av en Förtvålningsreaktion. Förtvålningen Fick ske vid 850 C under 2,5 timmar. Den så erhållna produkten tvättades med 5 % etanol/vatten, neutraliserades samt krymptes i etanol.The reaction mixture was added with a solution consisting of 50 g of sodium hydroxide and 225 g of water to effect a saponification reaction. The saponification had to take place at 850 C for 2.5 hours. The product thus obtained was washed with 5% ethanol / water, neutralized and shrunk in ethanol.
Produkten torkades i torkskåp vid 700 C under 15 timmar. erhöll därvid l95 g produkt med bäddvolymen l20 ml/g.The product was dried in a drying cabinet at 700 ° C for 15 hours. thereby obtained l95 g of product with a bed volume of 120 ml / g.
Man 5 g produkt enligt ovan skiktades på botten av en 100 ml bägare. Üver produkten skiktades 100 ml destillerat vatten. Det påförda vattnet absorberades på 49 sekunder.5 g of product as above were layered on the bottom of a 100 ml beaker. 100 ml of distilled water was layered over the product. The applied water was absorbed in 49 seconds.
Vid ett analogt försök utfört med en kommersiellt tillgänglig, förtvålad ymppolymer av stärkelse-polyakrylnitril (Polymer 35 - A - 100, Grain Processing Corporation, Muscatine, Iowa, USA) blev absorptionstiden 221 sekunder.In an analogous experiment performed with a commercially available, saponified starch polyacrylonitrile graft polymer (Polymer 35 - A - 100, Grain Processing Corporation, Muscatine, Iowa, USA), the absorption time was 221 seconds.
Vid ytterligare ett analogt försök utfört med en annan kommer- siellt tillgänglig, förtvålad ymppolymer av stärke1se-polyakryl- nitril (SGP 502 S, General Mills Chemicals Inc., USA) blev _ absorptionstiden 2400 sekunder.In another analogous experiment performed with another commercially available, saponified soap polymer of starch polyacrylonitrile (SGP 502 S, General Mills Chemicals Inc., USA), the absorption time was 2400 seconds.
Exexpel 2 200 g hydroxietylcellulosa (Natrosol 250 JR) samt 13 g hydroxi- etylcellulosa (Merck-Schuchardt, Kebo 15129) försattes med en lösning bestående av 1300 g destillerat vatten, 75 g natrium- hydroxid och 5 g natriumborhydrid. Hydroxietylcellulosan bringa- des i lösning genom omröring vid rumstemperatur. vsooszafs 6 "Den så erhållna lösningen fördes ner i en annan lösning bestående av l500 ml etylendiklorid och 105 g stabilisator (Bayer, Cellite 1 BP 900). Blandningen värmdes till 700 C under omröring och försattes med 35 ml epiklorhydrin.Examples 2,200 g of hydroxyethylcellulose (Natrosol 250 JR) and 13 g of hydroxyethylcellulose (Merck-Schuchardt, Kebo 15129) were added with a solution consisting of 1300 g of distilled water, 75 g of sodium hydroxide and 5 g of sodium borohydride. The hydroxyethylcellulose was brought into solution by stirring at room temperature. The solution thus obtained was taken up in another solution consisting of 1500 ml of ethylene dichloride and 105 g of stabilizer (Bayer, Cellite 1 BP 900). The mixture was heated to 700 DEG C. with stirring and added with 35 ml of epichlorohydrin.
Reaktionen fick ske under omröring vid 700 C i 5 timmar. Reak- tionsblandningen kyldes till 230 C och försattes med 7 liter aceton under omröring. Den bildade tvärbundna kolhydratpolvme- ren fick sedimentera, varefter överstående vätska dekanterades bort. Produkten tvättades med aceton och sedan med 50 % etanol/ vatten samt neutraliserades. Slutligen_krymptes produkten' i etanol och torkades i torkskåp vid 700 C i 12 tim. Härvid erhölls 176 g tvärbunden kolhydratpolymer med bäddvolymen 34 ml/g. 86 g tvärbundenïkolhvdratpolymer enligt ovan försattes med 2000 destillerat vatten, varefter blandningen värmdes till 300 C under omröring. Därefter tillsattes i tur och ordning 160 g akrylnitril samt en lösning av 8 g cerium-ammoniumnitrat i 88 g 0,1 N salpetersyra.The reaction was allowed to proceed with stirring at 700 DEG C. for 5 hours. The reaction mixture was cooled to 230 DEG C. and added with 7 liters of acetone with stirring. The formed crosslinked carbohydrate polymer was allowed to settle, after which the supernatant was decanted off. The product was washed with acetone and then with 50% ethanol / water and neutralized. Finally, the product was shrunk in ethanol and dried in a drying cabinet at 700 DEG C. for 12 hours. 176 g of crosslinked carbohydrate polymer with a bed volume of 34 ml / g were obtained. 86 g of crosslinked carbohydrate polymer as above were added with 2000 distilled water, after which the mixture was heated to 300 ° C with stirring. Then 160 g of acrylonitrile and a solution of 8 g of cerium ammonium nitrate in 88 g of 0.1 N nitric acid were added successively.
Reaktionen fick fortgå i 2,5 timmar under omröring. Reaktionsa blandningen_försattes sedan med en lösning av 96 g natriumhyd- roxid och 500 ml destillerat vatten för åstadkommande av en förtvålningsreaktion. Förtvålningen fick ske under omröring vid 900 C i 2,5 timmar. Reaktionsblandningen kyldes till' 250 C och försattes med lika volym etanol.The reaction was allowed to proceed for 2.5 hours with stirring. The reaction mixture was then added with a solution of 96 g of sodium hydroxide and 500 ml of distilled water to give a saponification reaction. The saponification was allowed to take place with stirring at 900 DEG C. for 2.5 hours. The reaction mixture was cooled to 250 DEG C. and added with an equal volume of ethanol.
Produkten avskildes på filter och tvättades med 5 % etanol/ destillerat vatten. Produkten neutraliserades och krymptesr i etanol samt torkades i torkskåp vid 700 C i 15 timmar. Man erhöll därvid 280 g produkt enligt uppfinningen med bäddvolymen so ml/g. ' Exempel 3 75 g hydroxipropylstärkelse (Farinex X 15 A, AB Stadex, Malmö) försattes med i tur och ordning 500 ml toluen samt 350 ml 7900528-6 7 destillerat vatten under omröring. Blandningen värmdes till 60° C och försattes med 10 ml 2 N saltsyra för åstadkommande av hydrolys. Hydrolysreaktionen fick fortgå under omröring vid 600 C under 4 timmar och 20 minuter. Hydrolysen avbröts genom tillsats av 40 ml 10 N natronlut.The product was filtered off and washed with 5% ethanol / distilled water. The product was neutralized and shrunk in ethanol and dried in a drying cabinet at 700 DEG C. for 15 hours. 280 g of product according to the invention with a bed volume of 1 ml / g were obtained. Example 3 75 g of hydroxypropyl starch (Farinex X 15 A, AB Stadex, Malmö) were added successively with 500 ml of toluene and 350 ml of distilled water with stirring. The mixture was heated to 60 ° C and added with 10 ml of 2 N hydrochloric acid to effect hydrolysis. The hydrolysis reaction was allowed to proceed with stirring at 600 DEG C. for 4 hours and 20 minutes. The hydrolysis was stopped by adding 40 ml of 10 N sodium hydroxide solution.
Temperaturen hos reaktionsblandningen sänktes till 550 C och 10 ml epiklorhydrin tillsattes för åstadkommande av tvärbind- ning av polymeren. Tvärbindningen fick ske under 15 timmar vid 550 C under omröring. Toluenet avskildes och produkten tvättades med vatten, neutraliserades, tvättades med destil- lerat vatten samt krymptes med etanol. Produkten torkades i torkskåp vid 700 C under 12 timmar._ Man erhöll därvid 62 g tvärbunden kolhydratpolymer med en bäddvolym av 36 ml/gram. 44 g av den tvärbundna kolhydratpolymeren enligt ovan försattes med 546 g destillerat vatten och värmdes till 300 C under om- röring.The temperature of the reaction mixture was lowered to 550 DEG C. and 10 ml of epichlorohydrin were added to crosslink the polymer. The crosslinking was allowed to proceed for 15 hours at 550 ° C with stirring. The toluene was separated and the product was washed with water, neutralized, washed with distilled water and shrunk with ethanol. The product was dried in a drying cabinet at 700 DEG C. for 12 hours. 62 g of crosslinked carbohydrate polymer with a bed volume of 36 ml / gram were obtained. 44 g of the crosslinked carbohydrate polymer as above were added with 546 g of distilled water and heated to 300 DEG C. with stirring.
Den så erhållna suspensionen försattes med i tur och ordning 40 g akrylnitril och 2,5 g cerium-ammoniumnitrat löst i 25 g 0,1 N salpetersyra. Reaktionen fick fortgå i 2,5 timmar under omröring.The suspension thus obtained was successively added with 40 g of acrylonitrile and 2.5 g of cerium ammonium nitrate dissolved in 25 g of 0.1 N nitric acid. The reaction was allowed to proceed for 2.5 hours with stirring.
Termostateringen var inställd på 300 C, men reaktionsbland- ningen antog 15 minuter efter satsningen av akrylnitril en temperatur av 400 C. Reaktionsblandningen försattes med-en lösning bestående av 25 g natriumhydroxíd och 100 ml destil- lerat vatten för åstadkommande av en förtvålningsreaktion.The thermostat was set at 300 DEG C., but the reaction mixture assumed a temperature of 400 DEG C. 15 minutes after the addition of acrylonitrile. The reaction mixture was added with a solution consisting of 25 g of sodium hydroxide and 100 ml of distilled water to effect a saponification reaction.
Förtvålningen fick ske vid 950 C under 2 timmar. Den så er- hållna produkten tvättades med 5 % etanol/vatten, neutrali- serades samt krymptes i etanol. Produkten torkades i tork- skåp vid 750 C i lztimmar. Man erhöll därvid ll5 g förtvålad produkt enligt uppfinningen med bäddvolymen ll3 ml/g.The saponification was allowed to take place at 950 ° C for 2 hours. The product thus obtained was washed with 5% ethanol / water, neutralized and shrunk in ethanol. The product was dried in a drying cabinet at 750 ° C for 1 hour. 115 g of saponified product according to the invention with a bed volume of 13 ml / g were obtained.
Uppfinningen är inte begränsad till de visade utföringsfor- merna, då dessa kan modifieras på olika sätt inom uppfin- ningens ram.The invention is not limited to the embodiments shown, as these can be modified in various ways within the scope of the invention.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE7900528A SE428211C (en) | 1979-01-22 | 1979-01-22 | A PARTICULATED ABSORPTION MATERIAL BASED ON A NITRIL IMPOLYMER AND A CROSS-BONDED CARBOHYDRATE POLYMER AND PROCEDURE FOR PREPARING IT |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE7900528A SE428211C (en) | 1979-01-22 | 1979-01-22 | A PARTICULATED ABSORPTION MATERIAL BASED ON A NITRIL IMPOLYMER AND A CROSS-BONDED CARBOHYDRATE POLYMER AND PROCEDURE FOR PREPARING IT |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| SE7900528L SE7900528L (en) | 1980-07-23 |
| SE428211B SE428211B (en) | 1983-06-13 |
| SE428211C true SE428211C (en) | 1986-05-20 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SE7900528A SE428211C (en) | 1979-01-22 | 1979-01-22 | A PARTICULATED ABSORPTION MATERIAL BASED ON A NITRIL IMPOLYMER AND A CROSS-BONDED CARBOHYDRATE POLYMER AND PROCEDURE FOR PREPARING IT |
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| Country | Link |
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| SE (1) | SE428211C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4950692A (en) * | 1988-12-19 | 1990-08-21 | Nalco Chemical Company | Method for reconstituting superabsorbent polymer fines |
| US4970267A (en) * | 1990-03-08 | 1990-11-13 | Nalco Chemical Company | Reconstitution of superabsorbent polymer fines using persulfate salts |
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1979
- 1979-01-22 SE SE7900528A patent/SE428211C/en not_active IP Right Cessation
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| Publication number | Publication date |
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| SE7900528L (en) | 1980-07-23 |
| SE428211B (en) | 1983-06-13 |
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