SI9700114A

SI9700114A - Process for the preparation of water-swelling polymers with an incorporated active ingredient

Info

Publication number: SI9700114A
Application number: SI9700114A
Authority: SI
Inventors: Primož Ogorelec; Branko Petrovič; Margareta Vrtačnik; Brouwer Nataša Zupančič; Aleksandra Krumpak; Vojko Škerlavaj
Original assignee: MELAMIN kemična tovarna d.d. Kočevje; PINUS tovarna kemičnih izdelkov d.d.
Priority date: 1997-05-05
Filing date: 1997-05-05
Publication date: 1998-12-31

Abstract

A process for the preparation of water-swelling polymers with an incorporated active ingredient is disclosed wherein monomers suitable for manufacturing superabsorbent polymers are polymerized in a common way, characterized in that the active ingredient is introduced during the polymerization when the macromolecular network structure of the water-swelling monomer is still being formed. The active ingredient is introduced during the polymerization before or after the addition of an initiator and before the addition of a cross-linking agent. As active ingredients preferably agriculturally or pharmaceutically active agents are incorporated. The obtained products have the property of controlled release of the active ingredient.

Description

Postopek za pripravo v vodi nabrekljivih polimerov z vezano učinkovinoProcess for the preparation of water-swellable polymers with a bound active ingredient

Področje tehnike, v katero spada izumFIELD OF THE INVENTION

Izum je s področja kemije polimerov in se nanaša na postopek za pripravo v vodi nabrekljivih polimerov, ki vsebujejo vezane učinkovine, kot učinkovine za industrijske, agrikulturne, gradbene, kozmetične in medicinske namene, zlasti fitofarmacevtske in farmacevtske učinkovine, ki se lahko počasi sproščajo pri uporabi, kot tudi na navedene polimere, dobljene po tem postopku. Pri izumu gre za specifičen polimer z vezanimi učinkovinami, ki so vezane v polimerno mrežo z vodikovimi vezmi in/ali intramolekularnimi interakcijami. Biološka učinkovitost vezanih snovi ostane nespremenjena.The invention relates to the field of polymer chemistry and relates to a process for the preparation of water-swellable polymers containing bound active substances as active substances for industrial, agricultural, construction, cosmetic and medical purposes, in particular plant protection and pharmaceutical substances which may be slowly released when used. , as well as those polymers obtained by this process. The invention is a specific polymer with bound active substances which are bound in a polymer network by hydrogen bonds and / or intramolecular interactions. The biological performance of the bound substances remains unchanged.

Stanje tehnikeThe state of the art

Superabsorbenti so produkti in spojine, ki so sposobne absorbirati tipično več kot 100-kratno količino vode glede na svojo maso. Za njihovo pripravo je znanih več različnih postopkov. Superabsorbente poliakrilamidnega ali poliakrilatnega tipa lahko pripravimo, kot je opisano npr. v patentih EP 101253, US 4535131, JP 87273283, EP 79840, JP 87193902 in EP 583177.Superabsorbents are products and compounds capable of absorbing typically more than 100 times the amount of water by weight. A number of different procedures are known for their preparation. Superabsorbents of the polyacrylamide or polyacrylate type can be prepared as described e.g. in patents EP 101253, US 4535131, JP 87273283, EP 79840, JP 87193902 and EP 583177.

Te produkte lahko uporabijo zlasti za pripravo okolju neškodljivih fitofarmacevtskih formulacij za zatiranje škodljivcev in bolezni v vodnih in zemeljskih sistemih.In particular, they can be used to prepare environmentally friendly plant protection formulations for pest and disease control in aquatic and terrestrial systems.

Znanih je nekaj postopkov za pripravo produktov z lastnostjo kontroliranega sproščanja ob uporabi superabsorbentov. Formulacije s kontroliranim sproščanjem učinkovine lahko pripravijo z intenzivnim mešanjem učinkovine ali zmesi več učinkovin in drugih dodatkov z že pripravljenim superabsorbentom, kot je predlagano za zaščito v WO 89/12449, WO 89/12450, WO 89/12451, EP 285404, EP 380448. Znano je, da ima lahko absorpcijski material učinkovine na svoji površini fiksirane v taljivi adhezivni plasti, kot je predlagano za zaščito v WO 93/22048. Učinkovine lahko fiksirajo na predhodno pripravljene granule, pri čemer se učinkovina vključi v membrano z difuzijsko kontrolirano hitrostjo prepustnosti, ki nastane z mešanjem prepustnega nabrekljivega polimera z manj prepustnim kondenzacijskim polimerom, kot je predlagano za zaščito v EP 0046136. Znano je tudi, da je fitofarmacevtska molekula kemijsko vezana na makromolekularno verigo v vodi nabrekljivega polimera s hidrolizabilnimi vezmi, kot navaja Issa, R., 1990, Sollaro, R., 1993. Sproščanje vezane učinkovine dosežejo ob ustreznih pogojih, t.j. temperaturi in/ali pH.There are several known processes for preparing controlled release products using superabsorbents. Controlled release formulations of the active ingredient can be prepared by intensively mixing the active ingredient or a mixture of several active ingredients and other additives with a pre-prepared superabsorbent as proposed for protection in WO 89/12449, WO 89/12450, WO 89/12451, EP 285404, EP 380448. It is known that the absorbent material of the active ingredient may have its surface fixed in the fusible adhesive layer as proposed for protection in WO 93/22048. The active ingredients can be fixed to pre-prepared granules, the active ingredient being incorporated into a membrane with a diffusion controlled permeability rate, which is formed by mixing a permeable swelling polymer with a less permeable condensing polymer, as proposed for protection in EP 0046136. It is also known that plant protection is a molecule chemically bound to a macromolecular chain in a water-swellable polymer with hydrolysable bonds, as stated by Issa, R., 1990; Sollaro, R., 1993. The release of the bound substance is achieved under suitable conditions, i. temperature and / or pH.

Opis rešitve tehničnega problema z izvedbenimi primeriDescription of solution to a technical problem with implementation examples

Sedaj smo ugotovili, da je mogoče vezati učinkovine v polimerno mrežno strukturo superabsorbenta z injiciranjem učinkovine v reakcijsko zmes v ustrezni stopnji sinteze polimera, v kateri je makromolekulska mreža v vodi nabrekljivega polimera še v procesu nastajanja.It has now been found that it is possible to bind the active ingredients to the polymer network structure of the superabsorbent by injecting the active substance into the reaction mixture at an appropriate stage of polymer synthesis, in which the macromolecular network in the water of the swellable polymer is still in the process of formation.

Prvi predmet izuma je torej postopek za pripravo v vodi nabrekljivih polimerov z vezano učinkovino, pri katerem na običajen način polimeriziramo monomere, primerne za izdelavo superabsorpcijskih polimerov, označen s tem, da učinkovino uvedemo med polimerizacijo, ko je makromolekulama mreža v vodi nabrekljivega polimera še v nastajanju.The first object of the invention is therefore a process for the preparation of water-swellable polymers with a bound active ingredient, in which the monomers suitable for the manufacture of superabsorbable polymers are conventionally polymerized, characterized in that the active ingredient is introduced during polymerization when the macromolecules are reticulated in the water of the swellable polymer. emerging.

Tipi polimerizacij, ki pridejo v poštev, so znani npr. iz SI-P 90 1 0485, iz US 3,387,063, izJP 62205101.The types of polymerizations that are suitable are known e.g. from SI-P 90 1 0485, from US 3,387,063, from Publication Number 62205101.

Učinkovine prednostno uvedemo pred dodatkom iniciatorja. Tako dosežemo večjo kapaciteto nabrekanja produkta in boljše lastnosti sproščanja.The active ingredients are preferably introduced prior to the addition of the initiator. This results in greater product swelling capacity and better release properties.

Prednostno jih uvedemo pred dodatkom premreževalnega sredstva, vedno pa pred zamreženjem polimerne zmesi.They are preferably introduced prior to the addition of the crosslinking agent, and always before crosslinking of the polymer mixture.

Superabsorpcijski polimeri v smislu izuma so sintetski organski polimeri, ki so trdni in hidrofilni, ki absorbirajo več kot 100-kratno količino vode glede na svojo maso. Na splošno lahko te superabsorpcijske polimere pripravimo na znan način iz akrilamidnih in/ali akrilnih ali metakrilnih monomerov, njihovih zmesi ali njihovih predkondenzatov ob uporabi različnih premreževalnih sredstev, kot so etilen glikol diakrilat, glicerol, glicidil metakrilat, Ν,Ν’-metilen-bis-akrilamid, etilendiamin, N-metilolmetakrilamid, etilen glikoldimetakrilat, poliglicerol polimetakrilat, 1,3,5triakrilolheksahidro-s-triazin, benzoin alkileter. Premreženje lahko poteka tudi z uporabo UV. Dobljeni polimeri spadajo v naslednje razrede, kot so: poliakrilamidi, delno hidrolizirani poliakrilamidi, premreženi ali cepljivi poliakrilamidi, poliakrilati in polimetakrilati in njihovi kopolimeri (t.j. kopolimer akrilamida in natrijevega ak3 rilata, cepljivi kopolimer hidroliziranega Škroba in poliakrilonitrila, hidrolizirani kopolimer natrijeve soli akrilamida/natrijevega akrilata, premreženi modificirani poliakrilamidi, premrežene akrilne smole).Superabsorption polymers of the invention are synthetic organic polymers that are solid and hydrophilic, absorbing more than 100 times the amount of water by weight. Generally, these superabsorption polymers can be prepared in a known manner from acrylamide and / or acrylic or methacrylic monomers, mixtures thereof or precondensates using various cross-linking agents such as ethylene glycol diacrylate, glycerol, glycidyl methacrylate, Ν, Ν'-methylene-bis -acrylamide, ethylenediamine, N-methylolmethacrylamide, ethylene glycoldimethacrylate, polyglycerol polymethacrylate, 1,3,5triacrylolhexahydro-s-triazine, benzoin alkyl ether. Crosslinking can also be done using UV. The resulting polymers fall into the following classes, such as: polyacrylamides, partially hydrolyzed polyacrylamides, cross-linked or fissionable polyacrylamides, polyacrylates and polymethacrylates and their copolymers (ie, copolymer of acrylamide and sodium acrylate acrylate acrylated acrylate acrylate) acrylates, cross-linked modified polyacrylamides, cross-linked acrylic resins).

Primerne učinkovine, formulacije sredstev in posamezne komponenete sredstev, ki jih lahko vežemo v polimerno mrežo zgoraj omenjenih polimerov, so insekticidi, herbicidi, fungicidi, akaricidi, nematocidi, avicidi, molluscicidi, rodenticidi, algicidi, biološka sredstva, natančneje ovicidi, larvicidi, limacidi, pupicidi, mikrobna kontrolna sredstva, patogeni, paraziti, regulatorji rasti rastlin, regulatorji rasti žuželk, sterilizacijska sredstva, koagulanti, atraktanti, repelenti, hormoni, feromoni in njihove zmesi kot tudi sredstva za vonj, sredstva za okus, antibakterijska sredstva, gnojila in njihove zmesi ali druge sestavine za kozmetične ali farmacevtske pripravke.Suitable ingredients, formulations and individual components of agents that can be bound into the polymer network of the above polymers are insecticides, herbicides, fungicides, acaricides, nematocides, avicides, molluscicides, rodenticides, algicides, biological agents, more specifically ovicides, larvicides pupicides, microbial control agents, pathogens, parasites, plant growth regulators, insect growth regulators, sterilizing agents, coagulants, attractants, repellents, hormones, pheromones and mixtures thereof as well as odors, flavoring agents, antibacterial agents, fertilizers and mixtures thereof or other ingredients for cosmetic or pharmaceutical preparations.

V vodi nabrekljivi polimeri z vezanimi učinkovinami, pripravljeni po tukaj opisanem postopku, so prav tako predmet izuma. Imajo lastnost kontroliranega sproščanja učinkovine. Pri postopku v smislu izuma za pripravo v vodi nabrekljivih polimerov z učinkovinami ni bistveno spremenjeno niti število stopenj kemijske sinteze niti trajanje priprave produkta v primerjavi s sintezo superabsorpcijskih polimerov istega polimernega tipa brez vezane učinkovine.Water-swollen polymers with bound active ingredients prepared by the process described herein are also an object of the invention. They have the property of controlled release of the active substance. In the process of the invention for the preparation of water-swellable polymers with active ingredients, neither the number of chemical synthesis steps nor the duration of product preparation is substantially altered compared to the synthesis of superabsorbent polymers of the same non-bound polymeric type.

Splošno je količina učinkovine, ki jo lahko vežemo v polimerni nosilec pri pripravi formulacije z mešanjem že pripravljenega polimera z učinkovino, zelo omejena zaradi majhne topnosti učinkovine v vodi; zaradi dodatka organskih topil, v katerih so topne učinkovine, in površinsko aktivnih snovi, ki sestavljajo formulacijo, pa se močno zmanjša stopnja nabrekanja polimernega nosilca. Tukaj opisani postopek omogoča, da med sintezo polimernega materiala vežemo relativno visoke koncentracije tako vodotopnih kot tudi zelo slabo vodotopnih učinkovin. Aktivnost spojin, vezanih v polimerno mrežo, se bistveno ne spremeni.In general, the amount of active ingredient that can be bound into a polymeric carrier when preparing a formulation by mixing an already prepared polymer with the active ingredient is very limited due to the low solubility of the active ingredient in water; however, the swelling of the polymeric carrier is greatly reduced by the addition of organic solvents containing the active ingredients and the surfactants that make up the formulation. The procedure described here allows the binding of relatively high concentrations of both water-soluble and very poorly water-soluble substances during the synthesis of the polymeric material. The activity of the compounds bound in the polymer network does not change significantly.

Vezava učinkovine med postopkom sinteze polimerne mreže superabsorbenta bistveno ne vpliva na kapaciteto nabrekanja končnega produkta v vodi v primerjavi s tržno dostopnimi, v vodi nabrekljivimi superabsorbenti brez vezanih učinkovin.The binding of the active ingredient during the synthesis process of the polymer superabsorbent network does not significantly affect the swelling capacity of the final product in water compared to commercially available water-swellable superabsorbents without bound active substances.

Visoke koncentracije učinkovin, vezanih v polimerno mrežo, pripravljeno po opisanem postopku, omogočajo podaljšanje učinkovitosti končnega produkta na osnovi kontroliranega sproščanja z znatnim zmanjšanjem nekotroliranega luženja učinkovine v okolje (vodo ali prst).The high concentrations of the active substances bound in the polymer network, prepared according to the described procedure, allow to prolong the efficacy of the final product on a controlled release basis with a significant reduction in the uncontrolled leaching of the active substance into the environment (water or soil).

Izum podrobneje pojasnjujejo naslednji izvedbeni primeri.The invention is further explained by the following embodiments.

Primer 1Example 1

Sinteza v vodi nabrekljivega polimera z vezanim O-2-dietilamino-6-metil-pirimidin4-il 0,0-dimetil fosforotionatom - pirimifos-metilom (pirimiphos-methyl)Synthesis of water-swellable polymer with bound O-2-diethylamino-6-methyl-pyrimidin4-yl 0,0-dimethyl phosphorothionate-pyrimiphos-methyl (pyrimiphos-methyl)

250,0 ml vode brez kisika, 28,0 g uprašenega natrijevega hidroksida in 50,0 ml akrilne kisline damo v bučo s štirimi vratovi, opremljeno z zatesnjenim mešalom, hladilnikom z dvojno površino, uvajalko za plinski dušik in termometrom. pH naravnamo na vrednost 5,9. Zmes mešamo ob stalnem dovajanju dušika. Ko temperatura reakcijske zmesi doseže 39°C, dodamo 100,0 g akrilamida, 8,0 g tehničnega pirimifos-metila, predhodno suspendiranega v 5,0 g zmesi tri-metil-substituiranih benzenov, in 0,5 g kalcijevega dodecilbenzensulfonata v zmesi z 0,2 g 2-metilpropanola, nato pa 0,5 g kalijevega persulfata kot radikalskega iniciatorja in 4 kapljice 33% vodne raztopine natrijevega hidrogensulfata(IV) kot ko-katalizatorja. Ko doseže viskoznost zmesi 500 mPa.s, dodamo 0,5 g premreževalnega sredstva Ν,Ν’-metilen-bis-akrilamida ob vzdrževanju reakcijske temperature pri 39°C. Po 2 minutah mešalo izklopimo, atmosfero dušika pa še vzdržujemo. Temperaturo dvignemo na 97°C. Po dveh urah produkt ohladimo in razrežemo na kocke s stranico 3 do 4 mm. Dobimo 440,0 g trdnega in nelepljivega svetlordečega, v vodi nabrekljivega produkta v obliki gela. Kapaciteta absorpcije vode suhega produkta je 183 g/g.250.0 ml of oxygen-free water, 28.0 g of powdered sodium hydroxide and 50.0 ml of acrylic acid are placed in a four-necked flask equipped with a sealed mixer, dual-surface cooler, gas nitrogen gas dispenser and thermometer. The pH was adjusted to 5.9. The mixture was stirred with a constant supply of nitrogen. When the temperature of the reaction mixture reached 39 ° C, 100.0 g of acrylamide, 8.0 g of technical pyrimiphos-methyl previously suspended in 5.0 g of a mixture of tri-methyl-substituted benzenes and 0.5 g of calcium dodecylbenzenesulfonate in a mixture with 0.2 g of 2-methylpropanol followed by 0.5 g of potassium persulfate as a radical initiator and 4 drops of 33% aqueous sodium hydrogen sulfate (IV) solution as co-catalyst. When the viscosity of the mixture was 500 mPa.s, 0.5 g of the crosslinking agent Ν, il-methylene-bis-acrylamide was added while maintaining the reaction temperature at 39 ° C. After 2 minutes the mixer is switched off and the nitrogen atmosphere is maintained. The temperature is raised to 97 ° C. After two hours, cool the product and cut it into cubes of 3 to 4 mm sides. 440.0 g of a solid, non-sticky, light red, water-swellable gel product are obtained. The water absorption capacity of the dry product is 183 g / g.

Primer 2Example 2

Sinteza v vodi nabrekljivega polimera z vezanim l-(bifenil-4-iloksi)-3,3-dimetil-l(lH-l,2,4-triazol-l-il)butan-2-olom (bitertanol)Synthesis of water-swollen polymer with bound 1- (biphenyl-4-yloxy) -3,3-dimethyl-1 (1H-1,2,4-triazol-1-yl) butan-2-ol (bitertanol)

250,0 ml vode brez kisika, 28,0 g uprašenega natrijevega hidroksida in 50,0 ml akrilne kisline damo v bučo s štirimi vratovi, opremljeno z zatesnjenim mešalom, hladilnikom z dvojno površino, uvajalko za plinski dušik in termometrom. pH naravnamo na vrednost 5,9. Zmes mešamo ob stalnem dovajanju dušika. Ko temperatura reakcijske zmesi doseže 39°C, dodamo 100,0 g akrilamida, 8,0 g tehničnega bitertanola, predhodno suspendiranega v 15,0 ml vode, in 0,5 g kalcijevega dodecilbenzensulfonata v zmesi z 0,2 g 2-metilpirolidona, nato pa 0,5 g kalijevega persulfata kot radikalskega iniciatorja in 4 kapljice 33% vodne raztopine natrijevega hidrogensulfata(IV) kot ko-katalizatorja. Ko doseže viskoznost zmesi 500 mPa.s, dodamo 0,5 g premreževalnega sredstva Ν,Ν’-metilen-bis-akrilamida ob vzdrževanju reakcijske temperature pri 38°C. Po 2 minutah mešalo izklopimo, atmosfero dušika pa še vzdržujemo. Temperaturo dvignemo na 103°C. Po dveh urah produkt ohladimo in razrežemo na kocke s stranico 3 do 4 mm. Dobimo 440,0 g trdnega in nelepljivega belega, v vodi nabrekljivega produkta v obliki gela. Kapaciteta absorpcije vode suhega produkta je 168 g/g.250.0 ml of oxygen-free water, 28.0 g of powdered sodium hydroxide and 50.0 ml of acrylic acid are placed in a four-necked flask equipped with a sealed mixer, dual-surface cooler, gas nitrogen gas dispenser and thermometer. The pH was adjusted to 5.9. The mixture was stirred with a constant supply of nitrogen. When the temperature of the reaction mixture reaches 39 ° C, 100.0 g of acrylamide, 8.0 g of technical bitertanol, previously suspended in 15.0 ml of water, and 0.5 g of calcium dodecylbenzenesulfonate in a mixture of 0.2 g of 2-methylpyrrolidone are added. followed by 0.5 g of potassium persulfate as the radical initiator and 4 drops of 33% aqueous sodium hydrogen sulfate (IV) solution as co-catalyst. When the viscosity of the mixture was 500 mPa.s, 0.5 g of the crosslinking agent Ν, il-methylene-bis-acrylamide was added while maintaining the reaction temperature at 38 ° C. After 2 minutes, the mixer is switched off and the nitrogen atmosphere is maintained. The temperature is raised to 103 ° C. After two hours, cool the product and cut it into cubes of 3 to 4 mm sides. 440.0 g of a solid, non-sticky white, water-swellable gel product are obtained. The water absorption capacity of the dry product is 168 g / g.

Primer 3Example 3

Sinteza v vodi nabrekljivega polimera z vezanim 4-metiltio-3,5-ksilil metilkarbamatom - metiokarbom (methiocarb)Synthesis of water-swellable polymer with bound 4-methylthio-3,5-xylyl methylcarbamate - methiocarb (methiocarb)

250,0 ml vode brez kisika, 28,0 g uprašenega natrijevega hidroksida in 50,0 ml akrilne kisline damo v bučo s štirimi vratovi, opremljeno z zatesnjenim mešalom, hladilnikom z dvojno površino, uvajalko za plinski dušik in termometrom. pH naravnamo na vrednost 5,9. Zmes mešamo ob stalnem dovajanju dušika. Ko temperatura reakcijske zmesi doseže 45°C, dodamo 100,0 g akrilamida, nato pa 0,5 g kalijevega persulfata kot radikalskega iniciatorja in 4 kapljice 33% vodne raztopine natrijevega hidrogensulfata(IV) kot ko-katalizatorja. Po 15 minutah takoj dodamo 8,0 g tehničnega metiokarba, suspendiranega v 15 ml vode, in 0,5 g kalcijevega dodecilbenzensulfonata v zmesi z 0,2 g 2-metilpirolidona. Ko doseže viskoznost zmesi 500 mPa.s, dodamo 0,5 g premreževalnega sredstva Ν,Ν’-metilen-bis-akrilamida ob vzdrževanju reakcijske temperature pri 45°C. Po 4 minutah mešalo izklopimo, atmosfero dušika pa še vzdržujemo. Temperaturo dvignemo na 70°C. Po dveh urah produkt ohladimo in razrežemo na kocke z dimenzijo 3 do 4 mm. Dobimo 440,0 g trdnega mehkega, nelepljivega brezbarvnega, v vodi nabrekljivega produkta v obliki gela. Kapaciteta absorpcije vode suhega produkta je 202 g/g.250.0 ml of oxygen-free water, 28.0 g of powdered sodium hydroxide and 50.0 ml of acrylic acid are placed in a four-necked flask equipped with a sealed mixer, dual-surface cooler, gas nitrogen gas dispenser and thermometer. The pH was adjusted to 5.9. The mixture was stirred with a constant supply of nitrogen. When the temperature of the reaction mixture reached 45 ° C, 100.0 g of acrylamide were added followed by 0.5 g of potassium persulfate as the radical initiator and 4 drops of 33% aqueous sodium hydrogen sulfate (IV) solution as co-catalyst. After 15 minutes, 8.0 g of technical methiocarb suspended in 15 ml of water were added immediately and 0.5 g of calcium dodecylbenzenesulfonate in a mixture with 0.2 g of 2-methylpyrrolidone. When the viscosity of the mixture was 500 mPa.s, 0.5 g of the crosslinking agent Ν, il-methylene-bis-acrylamide was added while maintaining the reaction temperature at 45 ° C. After 4 minutes, the mixer is switched off and the nitrogen atmosphere is maintained. The temperature is raised to 70 ° C. After two hours, the product was cooled and cut into cubes of 3 to 4 mm in size. 440.0 g of a solid soft, non-sticky, colorless, water-swellable gel product are obtained. The water absorption capacity of the dry product is 202 g / g.

Primer 4Example 4

Sinteza v vodi nabrekljivega polimera z vezanim propil-3-(dimetilamino)propilkarbamat hidrokloridom - propamokarbom (propamocarb)Synthesis of water-swellable polymer with bound propyl-3- (dimethylamino) propylcarbamate hydrochloride - propamocarb (propamocarb)

250,0 ml vode brez kisika, 28,0 g uprašenega natrijevega hidroksida in 50,0 ml akrilne kisline damo v bučo s štirimi vratovi, opremljeno z zatesnjenim mešalom, hladilnikom z dvojno površino, uvajalko za plinski dušik in termometrom. pH naravnamo na vrednost 5,9. Zmes mešamo ob stalnem dovajanju dušika. Ko temperatura reakcijske zmesi doseže 40°C, dodamo 100,0 g akrilamida in 4,8 g tehničnega propamokarba v 8,0 g zmesi metanola in vode (8:2), nato pa 0,5 g kalijevega persulfata kot radikalskega iniciatorja in 4 kapljice 33% vodne raztopine natrijevega hidrogensulfata(IV) kot ko-katalizatorja. Ko doseže viskoznost zmesi 500 mPa.s, dodamo 0,5 g premreževalnega sredstva Ν,Ν’-metilen-bis-akrilamida ob vzdrževanju reakcijske temperature pri 39°C. Po 2 minutah mešalo izklopimo, atmosfero dušika pa še vzdržujemo. Temperaturo dvignemo na 95°C. Po dveh urah produkt ohladimo in razrežemo na kocke s stranico 3 do 4 mm. Dobimo 440,0 g trdnega in nelepljivega brezbarvnega, v vodi nabrekljivega produkta v obliki gela. Kapaciteta absorpcije vode suhega produkta je 196 g/g.250.0 ml of oxygen-free water, 28.0 g of powdered sodium hydroxide and 50.0 ml of acrylic acid are placed in a four-necked flask equipped with a sealed mixer, dual-surface cooler, gas nitrogen gas dispenser and thermometer. The pH was adjusted to 5.9. The mixture was stirred with a constant supply of nitrogen. When the temperature of the reaction mixture reached 40 ° C, add 100.0 g of acrylamide and 4.8 g of technical propamocarb in 8.0 g of a mixture of methanol and water (8: 2) followed by 0.5 g of potassium persulfate as the radical initiator and 4 droplets of 33% aqueous sodium hydrogen sulfate (IV) solution as co-catalyst. When the viscosity of the mixture was 500 mPa.s, 0.5 g of the crosslinking agent Ν, il-methylene-bis-acrylamide was added while maintaining the reaction temperature at 39 ° C. After 2 minutes, the mixer is switched off and the nitrogen atmosphere is maintained. The temperature is raised to 95 ° C. After two hours, cool the product and cut it into cubes of 3 to 4 mm sides. 440.0 g of a solid, non-sticky, colorless, water-swellable gel product are obtained. The water absorption capacity of the dry product is 196 g / g.

Primer 5Example 5

Sinteza v vodi nabrekljivega polimera z vezanim O,O-dimetil-S-metilkarbamoilmetil fosforotionatom - ometoatom (omethoate)Synthesis of water-swollen polymer with bound O, O-dimethyl-S-methylcarbamoylmethyl phosphorothionate - ometoate (omethoate)

250,0 ml vode brez kisika, 28,0 g uprašenega natrijevega hidroksida in 50,0 ml akrilne kisline damo v bučo s štirimi vratovi, opremljeno z zatesnjenim mešalom, hladilnikom z dvojno površino, uvajalko za plinski dušik in termometrom. pH naravnamo na vrednost 5,9. Ko temperatura reakcijske zmesi doseže 40°C, dodamo 100,0 g akrilamida in 4,6 g tehničnega ometoata v 8,0 g metoksipropilacetata, nato pa 0,5 g kalijevega persulfata kot radikalskega iniciatorja in 4 kapljice 33% vodne raztopine natrijevega hidrogensulfata(IV) kot ko-katalizatorja. Ko doseže viskoznost zmesi 500 mPa.s, dodamo 0,5 g premreževalnega sredstva Ν,Ν’-metilen-bis-akrilamida ob vzdrževanju reakcijske temperature pri 38°C. Po 2 minutah mešalo izklopimo, atmosfero dušika pa še vzdržujemo. Temperaturo dvignemo na 92°C. Po dveh urah produkt ohladimo in razrežemo na kocke s stranico 3 do 4 mm. Dobimo 440,0 g trdnega in nelepljivega brezbarvnega, v vodi nabrekljivega produkta v obliki gela. Kapaciteta absorpcije vode suhega produkta je 155 g/g.250.0 ml of oxygen-free water, 28.0 g of powdered sodium hydroxide and 50.0 ml of acrylic acid are placed in a four-necked flask equipped with a sealed mixer, dual-surface cooler, gas nitrogen gas dispenser and thermometer. The pH was adjusted to 5.9. When the temperature of the reaction mixture reaches 40 ° C, add 100.0 g of acrylamide and 4.6 g of technical ometoate in 8.0 g of methoxypropyl acetate, followed by 0.5 g of potassium persulfate as the radical initiator and 4 drops of 33% aqueous sodium hydrogen sulfate ( IV) as a co-catalyst. When the viscosity of the mixture was 500 mPa.s, 0.5 g of the crosslinking agent Ν, il-methylene-bis-acrylamide was added while maintaining the reaction temperature at 38 ° C. After 2 minutes, the mixer is switched off and the nitrogen atmosphere is maintained. The temperature is raised to 92 ° C. After two hours, cool the product and cut it into cubes of 3 to 4 mm sides. 440.0 g of a solid, non-sticky, colorless, water-swellable gel product are obtained. The water absorption capacity of the dry product is 155 g / g.

Produkti, dobljeni po primerih 1 do 5, so primerni za direktno uporabo kot uvodoma omenjena sredstva.The products obtained from Examples 1 to 5 are suitable for direct use as the aforementioned agents.

Merjenje sproščanja učinkovin, vezanih v polimer, nabrekljiv v vodi, v vodno fazoMeasurement of release of active substances bound in a water-swellable polymer into the aqueous phase

Sproščanje vezanih učinkovin merimo na naslednji način:The release of bound substances is measured as follows:

V vodi nabrekljive polimere z vezanimi učinkovinami, ki smo jih dobili po zgoraj opisanem postopku, spiramo z vodo. Stehtano maso polimera suspendiramo v izmerjeni volumen destilirane vode (Tabela); suspenzijo nato odfiltriramo, učinkovino pa ekstrahiramo z diklorometanom; organski sloj delno uparimo in v preostanku s plinsko kromatografijo določimo količino učinkovine. Rezultati so podani v naslednji tabeli.The water-swollen polymers of the bound active ingredients obtained by the procedure described above are washed with water. The weighed mass of the polymer was suspended in the measured volume of distilled water (Table); the suspension is then filtered off and the active ingredient is extracted with dichloromethane; the organic layer was partially evaporated and the amount of the active ingredient was determined by gas chromatography. The results are given in the following table.

TabelaTable

Sproščanje vezane učinkovine iz polimera, nabrekljivega v vodi, v vodno fazoRelease of the bound substance from the water-swellable polymer into the aqueous phase

Primer Example m (g) m (g) učinkovina, vezana v polimer polymer-bound active substance število izpiranj number rinses celoten V (ml) vode whole In (ml) water celotna m (“s) sproščene učinkovine total m (“s) of active substance released 1 1 15.0 15.0 pyrimiphos- methyl pyrimiphos- methyl 1 1 500 500 2.7 2.7 1.22 1.22 2 2 600 600 4.5 4.5 2.03 2.03 3 3 750 750 5.4 5.4 2.42 2.42 4 4 850 850 5.7 5.7 2.56 0.84 2.56 0.84 2 2 20.0 20.0 bitertanol bitertanol 1 1 500 500 3.1 3.1 2 2 600 600 4.0 4.0 1.10 1.10 3 3 700 700 5.1 5.1 1.40 1.40 4 4 800 800 5.7 5.7 1.56 1.56 3 3 20.4 20.4 methiocarb methiocarb 1 1 550 550 12.9 12.9 3.48 3.48 2 2 650 650 19.6 19.6 5.27 5.27 3 3 750 750 28.6 28.6 7.70 7.70 4 4 850 850 31.0 31.0 8.37 8.37

*masni delež izprane učinkovine (%)* mass fraction of washed substance (%)

V posebnih eksperimentih, kjer je bil volumen vode, uporabljen za vsako izpiranje, zelo velik v primerjavi s fazo gela, smo ugotovili, da lahko učinkovine popolnoma izperemo iz polimerne faze v vodno fazo.In specific experiments where the volume of water used for each wash was very large compared to the gel phase, it was found that the active substances could be completely washed from the polymer phase to the aqueous phase.

Claims

A process for the preparation of water-swellable polymers with a bound active ingredient, in which the monomers suitable for the manufacture of superabsorbable polymers are conventionally polymerized, characterized in that the active substance is introduced during polymerization when the macromolecules are reticulated in the water of the swollen polymer.

Method according to claim 1, characterized in that the active ingredient is introduced during polymerization before or after the initiator is added and before the crosslinker is added.

Process according to claim 2, characterized in that the active ingredient is introduced during polymerization before the initiator is added.

Process according to Claims 1 to 3, characterized in that the water-swellable polymers are synthetic, organic organic polymers which are solid and hydrophilic and which can absorb more than 100 times the amount of water by weight.

5. A process according to claims 1 to 4, characterized in that agri-culture or pharmaceutically effective agents are preferably binded as active ingredients.

Process according to claims 1 to 5, characterized in that the synthesis is carried out at a temperature of from 35 to 60 ° C.

7. Water-swollen polymers having bound active substances, characterized in that they are prepared according to the method of claim 1.

8. The use of water-swollen bound active ingredient polymers according to claim 7 as controlled release formulations for industrial, agricultural, construction, cosmetic and medical purposes.