RO132657A2 - Collagenic hydrogels with encapsulated nutritive elements - Google Patents

Collagenic hydrogels with encapsulated nutritive elements Download PDF

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RO132657A2
RO132657A2 ROA201600966A RO201600966A RO132657A2 RO 132657 A2 RO132657 A2 RO 132657A2 RO A201600966 A ROA201600966 A RO A201600966A RO 201600966 A RO201600966 A RO 201600966A RO 132657 A2 RO132657 A2 RO 132657A2
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hydrogels
encapsulated
collagenic
mixture
hydrogel
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ROA201600966A
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Romanian (ro)
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Gabriel Zăinescu
Florica Luminiţa Albu
Rodica Roxana Constantinescu
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Institutul Naţional De Cercetare-Dezvoltare Pentru Textile Şi Pielărie - Sucursala Institutul De Cercetare Pielărie
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/20Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses

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Abstract

The invention relates to a process for preparing collagenic gels with encapsulated nutritive elements, meant to be used in agriculture, as fertilizers. According to the invention, the process comprises the hydrolysis of pelt wastes in 2...3.5% concentrated sulphuric acid dissolved in industrial water, together with 1.8...3.5% di-potassium phosphate, 0.5...1% boric acid and 1...2.4% urea, in an autoclave with double jacket and stirrer, at the temperature of 80...98°C, for 2.5...4.5 h, followed by addition of 10...15% acrylamide, 0.8...1% a linseed oil-based product for encapsulation of protein and nutritive substances, as well as magnesium carbonate for pH correction, to result in an elastic semitransparent collagenic hydrogel with encapsulated nutrients with jellylike appearance, with a pH in the range of 5.8...6.8.

Description

Domeniul tehnic in care poate fi folosita invențiaThe technical field in which the invention can be used

Invenția se refera la hidrogeluri colagenice obținute din deșeuri de piei gelatina din tabacarii cu elemente nutritive încapsulate si destinate utilizării ca ferilizatori in agricultura.The invention relates to collagen hydrogels obtained from waste of gelatin skins from tobacco boxes with encapsulated nutrients and intended for use as fertilizers in agriculture.

Biopolimerii de natura organica, reprezintă o sursa de materii prime pentru agricultura, întrucât compoziția deșeurilor proteice oferă suficiente elemente care sa imbunatateasca compoziția si remedierea solurilor degradate, iar plantele pot valorifica elemente ca: azot,fosfor,fier, bor, calciu, magneziu, sodiu, potasiu, etc.Biopolymers of an organic nature represent a source of raw materials for agriculture, as the composition of protein wastes offers sufficient elements to improve the composition and remediation of degraded soils, and plants can harness elements such as: nitrogen, phosphorus, iron, boron, calcium, magnesium, sodium , potassium, etc.

Descrierea stadiului actualDescription of the current stage

De la lucrările lui Wichterle si Lim (Clinical contact lens practice 1960) asupra hidrogelurilor pe baza de 2-hidroxietil metacrilat (HEMA), domeniul s-a dezvoltat continuu si se dezvolta in continuare exploziv, datorita aplicațiilor multiple si importante pe care hidrogelurile le au in special in medicina si farmacie, dar si in alte domenii cum este de exemplu agricultura.Since the work of Wichterle and Lim (Clinical contact lens practice 1960) on hydrogels based on 2-hydroxyethyl methacrylate (HEMA), the field has grown continuously and continues to develop explosively, due to the multiple and important applications that hydrogels have in particular. in medicine and pharmacy, but also in other fields such as agriculture.

Soluția tehnica Obținerea de hidrogeluri cu structura colagenica prin hidroliză deșeurilor de piei gelatina cu aplicații in agricultura este o noutate, avand in vedere ca structura colagenica este utilizata numai in medicina.The technical solution Obtaining hydrogels with collagen structure by hydrolysis of gelatin skins waste with applications in agriculture is a novelty, considering that collagen structure is used only in medicine.

Hidrogelurile ce au la baza biopolimeri, in comparație cu hidrogelurile pe baza de polimeri sintetici, prezintă avantajul biodegradabilitatii, biocompatibilitatii cat si a unui nivel de toxicitate scăzut (Gonzâlez N., et al.1992).Hydrogels based on biopolymers, compared to hydrogels based on synthetic polymers, have the advantage of biodegradability, biocompatibility as well as a low level of toxicity (Gonzâlez N., et al. 1992).

Rețelele multicomponente absorbante de tip hidrogel sunt materiale de ultimă generație, cu structură tridimensională și capacitate ridicată de gonflare (Pooley S. A. et al., 2010). Aplicațiile acestor materiale se diversifică, pătrunzând în ultimii ani în agricultura, industriile alimentară, farmaceutică, electrotehnică și electronică, în domeniul protecției mediului și cel al biomaterialelor.Hydrogel type absorbent multicomponent networks are state-of-the-art materials, with three-dimensional structure and high inflation capacity (Pooley S. A. et al., 2010). The applications of these materials are diversifying, penetrating in recent years in agriculture, food, pharmaceutical, electrotechnical and electronic industries, in the field of environmental protection and biomaterials.

Hidrogelurile prezintă o structură tridimensională distinctă si deși prezintă un conținut ridicat de apă, hidrogelurile sunt insolubile în apă din cauza structurii reticulate (fizic sau chimic), a legaturilor sferice sau cristaline.The hydrogels have a distinct three-dimensional structure and although they have a high water content, the hydrogels are insoluble in water due to the lattice structure (physical or chemical), spherical or crystalline bonds.

Hidrogelurile pot fi obținute prin două mecanisme principale: hidrogeluri cu legături covalente sau ireversibile și hidrogeluri cu legături reversibile sau fizice. Cea de-a doua categorie cuprinde subclase variate cum ar fi interacțiunile ionice (hidrogeluri reticulate ionic sau complexe polielectrolitice) și interacțiuni secundare (hidrogeluri „încâlcite”, hidrogeluri grefate sau complexate, etc.) (Hennink W. E.et al.,2002). Domeniul sintezei hidrogelurilor a fost lărgit prin introducerea de polimeri naturali sau compozite dintre polimerii naturali și sintetici si se dezvolta in continuare exploziv, datorita aplicațiilor multiple si importante pe care hidrogelurile le au in special in medicina si farmacie, dar si in alte domenii cum este de exemplu agricultura. Hidrogelurile pot fi aplicate îri agricultură fie pentru păstrarea apei în sol sau eliberarea controlată a pesticidelor sau fertilizatorilor (Azeem, B. et al., 2014). în primul caz, aplicația se bazează pe capacitatea hidrogelurilor de a absorbi rapid o cantitate mare de apă și de a o elibera apoi treptat, asigurând alimentarea plantelor cu apă o perioadă mai îndelungată după ce udarea terenului (ploaie sau irigații) a încetat. Hidrogelurile ca sisteme cu eliberare controlată a fertilizatorilor în agricultură prezintă avantajul major că îmbină în același dispozitiv proprietatea de a absorbi apa și de a o elibera apoi lent în intervalul dintre ploi sau dintre irigații. Au deciHydrogels can be obtained by two main mechanisms: covalent or irreversible linkage hydrogels and reversible or physical linkage hydrogels. The second category comprises various subclasses such as ionic interactions (ionic crosslinked hydrogels or polyelectrolyte complexes) and secondary interactions ("entangled" hydrogels, grafted or complexed hydrogels, etc.) (Hennink W. E. et al., 2002). The field of synthesis of hydrogels has been expanded by introducing natural or composite polymers between natural and synthetic polymers and continues to develop explosively, due to the multiple and important applications that hydrogels have especially in medicine and pharmacy, but also in other fields such as for example agriculture. Hydrogels can be applied to agriculture either for keeping water in the soil or for the controlled release of pesticides or fertilizers (Azeem, B. et al., 2014). In the first case, the application is based on the ability of the hydrogels to quickly absorb a large amount of water and then release it gradually, providing the plants with water for a longer period after watering the land (rain or irrigation) has ceased. Hydrogels as systems with controlled release of fertilizers in agriculture have the major advantage that they combine in the same device the property of absorbing water and then releasing it slowly in the interval between rain or irrigation. So they have

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06/12/2016 capacitatea de stocare a apei în sol, având proprietatea de a elibera lent îngrășământul la rădăcina plantelor, cu avantajele incontestabile prezentate anterior. Din această cauză, încapsularea îngrășămintelor în hidrogeluri cu capacitate mare de absorbție a apei a început să fie cercetată mai intens în ultimi ani, deși lucrările publicate sunt încă puțin numeroase, mai ales, în domeniul polimerilor biodegradabili.06/12/2016 the capacity of water storage in the soil, having the property of slowly releasing the fertilizer at the root of the plants, with the indisputable advantages presented previously. For this reason, the encapsulation of fertilizers in hydrogels with high water absorption capacity has begun to be investigated more intensively in recent years, although the published works are still very few, especially in the field of biodegradable polymers.

Din studiul literaturii privind hidrogelurile cu aplicații la eliberarea controlată a fertilizanților (HECF) se pot desprinde câteva observații privind modul de sinteză, structura, modul de eliberare a fertilizantului, etc. Din punct de vedere al procedeului de sinteză, HECF au fost obținute: în soluție, în emulsie inversă, prin dispersarea soluției apoase de monomeri într-un solvent organic nemiscibil cu apa. Metoda prezintă avantaje tehnologice evidente, deoarece HECF se obțin direct sub formă de particule.în funcție de structura particulei de îngrășământ rezultate, hidrogelul poate forma: matricea în care este înglobat fertilizantul sau stratul acoperitor în care este învelit fertilizantul solid (Monica Puccini et al., 2015).Ca exemple de sinteza a unor hidrogeluri cu utilizări în agricultură se pot menționa: un hidrogel pe bază de amidon, carboximetil celuloză (CMC) și poliacrilamidă reticulată, obtinut prin polimerizarea radicalică în soluție apoasă a acrilamidei în prezența Ν,Ν'-metilenbisacrilamidei (MBA), ca agent de reticulare (Abd El-Rehim H. A. et al., 2006).From the study of the literature on hydrogels with applications to controlled fertilizer release (HECF), we can derive some observations regarding the synthesis mode, structure, fertilizer release mode, etc. From the point of view of the synthesis process, HECF were obtained: in solution, in reverse emulsion, by dispersing the aqueous solution of monomers in an organic solvent immiscible with water. The method has obvious technological advantages, because HECF is obtained directly as a particle. Depending on the structure of the resulting fertilizer particle, the hydrogel can form: the matrix in which the fertilizer is embedded or the coating layer in which the solid fertilizer is coated (Monica Puccini et al. Examples of the synthesis of hydrogels for agricultural use may be mentioned: a starch-based hydrogel, carboxymethyl cellulose (CMC) and cross-linked polyacrylamide, obtained by radical polymerization in aqueous acrylamide solution in the presence of Ν, Ν ' -methylenbisacrylamide (MBA), as a cross-linking agent (Abd El-Rehim HA et al., 2006).

Hidrogeluri cu aplicații în agricultură au fost obținute si prin reacții polimer analoage. De exemplu: in 2004 (Katime l.,et al.,2004) s-a utilizat reacția dintre alcoolul polivinilic si acidul fosforic în soluție apoasă, urmată de neutralizarea cu carbonat de sodiu. A rezultat un hidrogel reticulat prin punți fosfatice și având grupe laterale fosfat de sodiu care are capacitatea de a elibera lent grupe fosfat în mediu apos/umed. Alti cercetători au obținut hidrogeluri de tip amidon - alginat de sodiu prin amestecarea soluțiilor apoase ale acestor polimeri, care sunt hidrogeluri de tip compozit cu aplicații în agricultură. Hidrogelurile compozite au fost utilizate atât în calitate de matrice, cât și ca strat acoperitor al particulei de îngrășământ (Gao, Li, et al. 2015).Hydrogels with applications in agriculture were also obtained by analogous polymer reactions. For example: in 2004 (Katime l., Et al., 2004) the reaction between polyvinyl alcohol and phosphoric acid in aqueous solution was used, followed by neutralization with sodium carbonate. It resulted in a hydrogel cross-linked by phosphatic bridges and having sodium phosphate side groups which has the ability to slowly release phosphate groups in aqueous / wet medium. Other researchers have obtained starch - sodium alginate hydrogels by mixing aqueous solutions of these polymers, which are composite hydrogels for agricultural applications. Composite hydrogels have been used both as a matrix and as a coating for the fertilizer particle (Gao, Li, et al. 2015).

Invenția prezintă cercetările exploratorii care au ca punct de plecare obținerea de noi produse complexe - multicomponente polimerice - denumite hidrogeluri colagenice cu nutrienti încapsulați, prin prelucrarea deșeurilor de piei gelatina cu aplicații in horticultura.The invention presents the exploratory researches that have as a starting point the obtaining of new complex products - polymeric multicomponents - called collagenic hydrogels with encapsulated nutrients, by processing the waste of gelatin skins with applications in horticulture.

Descrierea detaliata a invenției în prezenta invenție, s-au utilizat deșeuri de piei cenușărite (depărate) provenite de la decărnarea și ștuțuirea pieilor de bovine (tip de greutate 35 kg), de la tăbăcăria SC Pielorex Jilava, jud. Ilfov Romania. S-a propus un procedeu inovativ si anume o hidroliză directa a deșeurilor de piei gelatina în mediu acid, în combinație cu alți polimeri (poliacrilamidă, amidon, acrilic, maleic, uree, celuloză, etc.) obtinandu-se hidrogeluri cu structura colagenica cu elemente nutritive încapsulate.Detailed description of the invention in the present invention was used ash (debris) skins from the scraping and stamping of cattle skins (type 35 kg weight), from the SC Pielorex Jilava tavern, Ilfov county Romania. An innovative process has been proposed, namely a direct hydrolysis of gelatin skin waste in acidic environment, in combination with other polymers (polyacrylamide, starch, acrylic, maleic, urea, cellulose, etc.) obtaining hydrogels with collagenic structure with nutrients encapsulated.

Invenția este explicata in detaliu prin următoarele exemple:The invention is explained in detail by the following examples:

Exemplul 1Example 1

Se cântăresc 3500 g deseu de piei gelatina, se spala si se decalcifica cu 4-4,5 % sulfat de amoniu si se adauga 2-3,5 % H2SO4 concentrat dilzolvat in 2-2,5 I apa industriala. Apoi se dizolva in 2 I apa industriala următoarele: 1,8-3,5% fosfat dipotasic (K2HPO4.3H2O), 0,5 -1 % acid boric (H3BO3) si 1-2,4 % uree; amestecul se supune unei hidrolize directe intr-o autoclava de 50 I cu dubla manta si agitator, la temperatura de 80-98°C timp de 2,5 - 4,5 ore.Weigh 3500 g of gelatin skin waste, wash and decalcify with 4-4.5% ammonium sulphate and add 2-3.5% H 2 SO 4 concentrated diluted in 2-2.5 I industrial water. Then 2 liters of water are dissolved in the following industries: 1.8 to 3.5% dipotassium hydrogen phosphate (K 2 HPO 4 .3H 2 O), 0.5 1% boric acid (H3BO3) and 1-2.4% urea ; the mixture is subjected to a direct hydrolysis in a 50 l autoclave with a double coat and shaker, at 80-98 ° C for 2.5 - 4.5 hours.

Pentru obținerea încapsulării proteinei a fost adaugat 0,8-1% produs EZ, pe baza de amestec de uleiuri vegetale (preponderent fiind uleiul de in), deci produs natural.To obtain the protein encapsulation, 0.8-1% EZ product was added, based on a mixture of vegetable oils (mainly flax oil), so it is a natural product.

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06/12/2016 b12/6/2016 b

încapsularea a fost realizata si demonstrata atat prin microscopie optica cat si prin expunerea la soare (timp de 67 de zile), constatându-se ca proteina nu a suferit transformări in special in ceea ce privește degradarea (nu miroase urat). Corecția pH-ului se face cu carbonat de magneziu MgCO3.The encapsulation was performed and demonstrated both by optical microscopy and by exposure to the sun (for 67 days), finding that the protein did not undergo transformations especially in terms of degradation (no foul odors). The pH correction is done with MgCO 3 magnesium carbonate.

A rezultat un hidrogel ureio-colagenic, gelatinos, reticulat cu pH de 5,8-6,5.A gelatinous urea-collagenic hydrogel resulted in a pH of 5.8-6.5.

Exemplu 2Example 2

Se cântăresc 6800 g deseu de piei gelatina, se spala si se decalcifica cu 4 - 4,5 % sulfat de amoniu si apoi se dilzolva in 5-6,5 I apa industriala urmatoarele:2-3,5 % H2SO4 concentrat, 2,5-3,5% fosfat dipotasic (K2HPO4.3H2O) si 0,5 -1 % sare industriala (NaCI) amestecul se toarna intr-o autoclava de 50 I cu dubla manta si agitator, la temperatura de 80-98°C timp de 2,5 - 4,5 ore. Apoi se adauga 10-15 % acrilamida(CH2=CH-CONH2) cu formare de persulfat de amoniu, inițiatorul reacției de reticulare. Pentru obținerea încapsulării proteinei si a elementelor nutritive a fost adaugat 0,8-1% un produs denumit EZ pe baza de amestec de uleiuri vegetale. Corecția pH-ului se face cu carbonat de magneziu MgCO3.Weigh 6800 g of gelatin skin waste, wash and decalcify with 4 - 4.5% ammonium sulphate and then dilute in 5-6.5 I industrial water the following: 2-3.5% concentrated H2SO4, 2, 5-3.5% dipotassium phosphate (K2HPO4.3H2O) and 0.5-1% industrial salt (NaCl) the mixture is poured into a 50 L autoclave with double cloak and shaker, at 80-98 ° C for 2.5 - 4.5 hours. Then 10-15% acrylamide (CH2 = CH-CONH2) with ammonium persulfate formation, the initiator of the cross-linking reaction, was added. To obtain the encapsulation of protein and nutrients, 0.8-1% was added a product called EZ based on a mixture of vegetable oils. The pH correction is done with MgCO 3 magnesium carbonate.

A rezultat un hidrogel colagenic cu nutrienti încapsulați, gelatinos, elastic si semitransparent, cu pH de 5,8-6,8.The result was a collagen hydrogel with encapsulated, gelatinous, elastic and semi-transparent nutrients, with a pH of 5.8-6.8.

Hidrogelurile colagenice cu elemente nutritive încapsulate, astfel obținute se livrează in stare gelatinoasa sau uscata, ambalate in butoaie de plastic sau in saci de polietilena insotite de instrucțiuni de utilizare.Collagen hydrogels with encapsulated nutrients, thus obtained, are delivered in a gelatinous or dry state, packed in plastic barrels or polyethylene bags accompanied by instructions for use.

Prin acest brevet se poate stabili o tehnologie de conversie a deșeurilor de piei gelatina in hidrogeluri colagenice cu elemente nutritive încapsulate, care pot fi folosiți ca fertilizatori in agricultura (in special in horticultura).This patent can establish a technology for converting gelatin waste into collagen hydrogels with encapsulated nutrients, which can be used as fertilizers in agriculture (especially in horticulture).

Claims (3)

1. Hidrogelul ureio - colagenic, cu elemente nutritive încapsulate, caracterizat prin aceea ca, o cantatitate de 3500 g deseu de piei gelatina, se spala si se decalcifica cu 4-4,5 % sulfat de amoniu si se adauga 2-3,5 % H2SO4 concentrat dilzolvat in 22,5 I apa industriala, apoi se dizolva in 2 I apa industriala următoarele: 1,8-3,5% fosfat dipotasic (K2HPO4.3H2O), 0,5 -1 % acid boric (H3BO3) si 1-2,4 % uree si amestecul se supune unei hidrolize directe intr-o autoclava de 50 I cu dubla manta si agitator, la temperatura de 80-98°C timp de 2,5 - 4,5 ore, apoi se adauga 0,8-1% produs EZ, pe baza de amestec de uleiuri vegetale,iar corecția pH-ului (pana la 5,8-6,5 ) se face cu carbonat de magneziu MgCC>3.1. The urea-collagen hydrogel, with encapsulated nutrients, characterized by the fact that a quantity of 3500 g of gelatin skins washes and is decalcified with 4-4.5% ammonium sulphate and added 2-3.5 % H 2 SO 4 concentrate diluted in 22.5 l of industrial water, then the following is dissolved in 2 l of industrial water: 1.8-3.5% dipotassium phosphate (K 2 HPO4.3H 2 O), 0.5 -1 % boric acid (H3BO3) and 1-2.4% urea and the mixture is subjected to a direct hydrolysis in a 50 l autoclave with double mantle and shaker, at 80-98 ° C for 2.5-4, 5 hours, then 0.8-1% EZ product is added, based on a mixture of vegetable oils, and the pH correction (up to 5.8-6.5) is made with MgCC> 3 magnesium carbonate. 2. Hidrogel colagenic cu nutrienti încapsulați, caracterizat prin aceea ca, o cantatitate de 6800 g deseu de piei gelatina, se spala si se decalcifica cu 4-4,5 % sulfat de amoniu si apoi se dilzolva in 5 - 6,5 I apa industriala urmatoarele:2-3,5 % H2SO4 concentrat, 2,5-3,5% fosfat dipotasic (K2HPO4.3H2O) si 0,5 -1 % sare industriala (NaCI) amestecul se toarna intr-o autoclava de 50 I cu dubla manta si agitator, la temperatura de 80-98°C timp de 2,5 - 4,5 ore, apoi se adauga 10-15 % acrilamida(CH2=CH-CONH2) si 0,8-1% produs EZ, pe baza de amestec de uleiuri vegetale, corecția pH-ului se face cu carbonat de magneziu MgCC>3, rezultând un hidrogel colagenic cu nutrienti încapsulați, cu aspect gelatinos, elastic si semitransparent, cu pH-ul in jur de 5,8-6,8.2. Collagen-containing hydrogel with encapsulated nutrients, characterized by the fact that a quantity of 6800 g of gelatin skin washes, is washed and decalcified with 4-4.5% ammonium sulphate and then diluted in 5 - 6.5 l of water. industrial following: 2-3.5% H 2 SO 4 concentrate, 2.5-3.5% dipotassium hydrogen phosphate (K 2 HPO 4 .3H 2 O) and 0.5 -1%, industrial salt (NaCl) and the mixture is poured in a 50 L autoclave with double coat and shaker, at 80-98 ° C for 2.5 - 4.5 hours, then add 10-15% acrylamide (CH 2 = CH-CONH 2 ) and 0.8-1% EZ product, based on a mixture of vegetable oils, the pH correction is made with magnesium carbonate MgCC> 3, resulting in a collagenic hydrogel with encapsulated nutrients, gelatinous, elastic and semi-transparent, with pH- ul around 5.8-6.8. 3. Hidrogeluri colagenice cu elemente încapsulate conform revendicărilor 1 si 2, caracterizat prin aceea ca, se pot livra in stare gelatinoasa sau uscata, putând fi folosite ca fertilizatori in agricultura (in special in horticultura).Collagenic hydrogels with encapsulated elements according to claims 1 and 2, characterized in that they can be delivered in a gelatinous or dry state, and can be used as fertilizers in agriculture (especially in horticulture).
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US12329077B2 (en) 2022-04-21 2025-06-17 Cori BYRGE Aquaponics plant production system

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US12329077B2 (en) 2022-04-21 2025-06-17 Cori BYRGE Aquaponics plant production system

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