WO1999007654A1

WO1999007654A1 - Encapsulated fertilizers

Info

Publication number: WO1999007654A1
Application number: PCT/IL1998/000322
Authority: WO
Inventors: Arie Markus; Zeev Wiesman; David Wolf
Original assignee: Ben Gurion University Of The Negev Research And Development Authority
Priority date: 1997-08-07
Filing date: 1998-07-09
Publication date: 1999-02-18
Also published as: EP1012129A1; IL121496A0; IL121496A; NZ502497A; CA2299334A1; AU741233B2; AU8239098A

Abstract

The invention provides a controlled-release encapsulated fertilizer comprising a core containing at least one fertilizer and a polymeric envelope containing at least one hormone encapsulating said fertilizer.

Description

ENCAPSULATED FERTILIZERS

Technical Field

The present invention relates to controlled-release encapsulated fertilizer. More particularly, the present invention relates to a controlled-release encapsulated fertilizer comprising a core containing at least one fertilizer and a polymeric envelope containing at least one hormone encapsulating said fertilizer Background Art

The encapsulating of various chemical reagents, pharmaceuticals, pesticides and herbicides in general have been proposed and described in the prior art.

As described e.g. in U. S. Patent 4,417,916, aqueous dispersions of pesticide and herbicide micro-capsules are particularly useful in controlled release pesticidal and herbicidal formulations because they can be diluted with water or liquid fertilizer and sprayed using conventional equipment, thereby producing uniform field coverage of the pesticide or herbicide/additives such as film forming agents can be added directly to the finished formulation to improve the adhesion of micro-capsules to foliage. In some cases, reduced toxicity and extended activity of encapsulated herbicides and pesticides have been noted.

A variety of techniques have heretofore been used or proposed for encapsulation purposes. In one such process, known as "simple co-acervation", a polymer separates from a solvent solution of the polymer by the action of a precipitating agent that reduces the solubility of the polymer in the solvent (e.g., a salt or a non-solvent for the polymer). Patents describing such processes and their shell wall material includes U. S. Patent Nos. 2,800,458 (hydrophilic colloids); 3,069,370 and 3,116,216 (polymers); 3,137,631 (denatured proteins); 3,418,250 (hydrophobic thermoplastic resins); and others.

Another method involves micro-encapsulation based on in situ interfacial condensation polymerization. British Patent No. 1 ,371 ,179 discloses a process which consists of dispersing an organic pesticide phase containing a poiymethyiene polyphenylisocyanate or toluylene diisocyanate monomer into an aqueous phase. The wall forming reaction is initiated by heating the batch to an elevated temperature at which point the isocyanate monomers are hydrolyzed at the interface to form amines, which in turn react with unhydrolyzed isocyanate is the possibility of continued reaction of monomer after packaging. Unless all monomer is reacted during the preparation, there will be continued hydrolysis of the isocyanate monomer with evolution of CO₂, resulting in the development of pressure when the formulation is packaged.

Various methods of encapsulation by interfacial condensation between direct-acting, complimentary reactions are known. Within these methods are reactions for producing various types of polymers as the capsule walls. Many of such reactions to reproduce the coating substance occur between an amine, which must be of at least di-functional character and a second reactant intermediate, which for producing a polyurea is a di-functional or polyfunctional isocyanate. The amines chiefly used or proposed in these methods are typified by ethylene diamine, having at least two primary amino groups. U. S. Patent No. 3,429,827 and U. S. Patent No. 3,577,515 are illustrative of encapsulation by interfacial condensation.

For example, U. S. Patent No. 3,577,515 describes a continuous or batch method which requires a first reactant and a second reactant complimentary to the first reactant, with each reactant in separate phases, such that the first and second reactants react at the interface between the droplets to form encapsulated droplets. The process is applicable to a large variety of polycondensation reactions, i.e., to many different pairs of reactants capable of interfacial condensation from respective carrier liquids to yield solid film at the liquid interface. The resulting capsule skin may be produced as a polyamide, polysulfonamide, polyester, polycarbonate, polyurethane, polyurea or mixtures of reactants in one or both phases so as to yield corresponding condensation copolymers. The reference describes the formation of a polyurea skin when diamines or polyamines (e.g. ethylene diamine, phenylene diamine, toluylene diamine, hexamethylene diamine and the like) are present in the water phase and di-isocyanates or polyisocyanates (e.g., toluene diisocyanate, hexamethylene diisocyanate and poiymethyiene polyphenylisocyanate) are present in the organic/oil phase.

Several methods for coating fertilizers of such as KNO₃ and NPK have been known. Until 1981 one patent by "Sierra" disclosed the coating of osmocote (NPK). After 1981 Japanese patents Nos. 84-146,053 and 54-840,716 disclosed coated fertilizers, said fertilizers were coated with urea formaldehyde. JP 63-162,593 discloses a fertilizer envelope. Said envelope is produced by spraying a solution of polyethylene and eva (ethyl vinyl acetate) in CC1₂=CC1₂ on fertilizer granules.

The world's nursery industry utilizes numerous products and techniques in order to maintain and produce millions of ornamental plants and fruit trees. The nursery industry uses sophisticated agrotechnologies and consumes large quantities of rooting stimulators. There is an ongoing need for novel products that could increase rooting percentages of difficult-to-root (mainly woody or semi-woody plant species) plants. There is also the need for improving the growth rate and quality of the plants produced by the nurseries.

A common procedure in a nursery entails the sporadic addition of fertilizers and hormones to the roots of new cuttings. The present inventors have found that the addition of a controlled-release encapsulated fertilizer can maintain the presence of the necessary compounds for the entire period of rooting and development of rooted plants. Disclosure of the Invention

With this state of the art in mind, there has now been found, according to the present invention, a controlled-release encapsulated fertilizer comprising a core containing at least one fertilizer and a polymeric envelope containing at least one hormone encapsulating said fertilizer.

In preferred embodiments of the present invention said envelope contains at least one hormone selected from the group consisting of Auxin; indole alkyl acid; indole acetic acid(IAA); indole propionic acid(IPA); indole butyric acid(IBA); 2,4 dichlorophenoxy acetic acid; 2,4 chlorophenoxy propionic acid; 2,4 dichloro phenoxyacetic acid propyl ester; and, Naphthalene acetic acid.

In another embodiment of the present invention there is provided a process for encapsulating a fertilizer comprising: a) coating a fertilizer with a mixture of a first monomer and a hormone; b) adding a mixture of a second monomer and additional a hormone; and, c) heating said mixtures to induce the polymerization of said first and second monomers to form a polymeric envelope incorporating said hormone and encapsulating said fertilizer. wherein said envelope contains at least one hormone selected from the group consisting of Auxin; indole alkyl acid; indole acetic acid(IAA); indole propionic acid(IPA); indole butyric acid(IBA); 2,4 dichlorophenoxy acetic acid; 2,4 chlorophenoxy propionic acid; 2,4 dichloro phenoxyacetic acid propyl ester; and, Naphthalene acetic acid. wherein said polymeric envelope is formed by a polymer selected from the group consisting of polyurethane; polyurea; and, polyolefins.

While the invention will now be described in connection with certain preferred embodiments in the following examples so that aspects thereof may be more fully understood and appreciated, it is not intended to limit the invention to these particular embodiments. On the contrary, it is intended to cover all alternatives, modifications and equivalents as may be included within the scope of the invention as defined by the appended claims. Thus, the following examples which include preferred embodiments will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of example and for purposes of illustrative discussion of preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of formulation procedures, as well as of the principles and conceptual aspects of the invention. Description of Preferred Embodiments Examples:

A series of formulations were prepared according to the present invention. As stated, according to the invention the fertilizer is the core of the formulation and the hormone is incorporated in the envelope. The hormones that were incorporated in the slow release formulations were from the following families: • Auxin- Indole alkyl acid IAA (Indole alkyl acid) ,

IPA (Indole Propionic Acid) and IBA (Indole Butynic Acid)

2,4 Dichlorophenoxy acetic acid

2,4 Dichlorophenoxy acetic propionic acid 2,4 Dichloro phenoxyacetic acetic acid propyl ester

Naphthalene acetic acid (NAA) auxin stimulated root regeneration and development

• Triazole - Paclobutrazole (growth retardant that has an anti- gibberllin-enhanching effect on stimulation of root formation and increasing survival of rooted pland grown in stress conditions.

• Cytokinine - Benzoyladenine (plant hormone that stimulates development and branching of shoots)

The coating consists of the following families of polymers:

• polyurethane

• polyurea

• polyolefis (like polyethylene) etc

Carbohydrates such as sucrose, starch, etc. that are enhancing auxin effect on stimulation of root regeneration and development are added to the envelope. Other materials that are added to the formulation are to increase the nutritional content (micro elements such as: Fe, B, Mg, Zn, Mn, Ca, Mo, etc.), to increase biotic tolerance (Benedate), Falpane, Merpan, Prochloraz, propionazol, diazinone, nephorex, etc), and to increase a biotic tolernace of the plants (triazole compounds such as majic that increase drought resistance by stimulation of wax cover of the leaves).

The above mentioned hormones increase the rate of cell division and differentiation and the result of said increased rate is a stimulation of root regeneration and development.

Growth retardants such as Triazole e.g. paclobutrazole can also be added. Said retardant has an anti-gibberllin-enhancing auxin effect on stimulation of root formation. Other materials that are added to the formulation are to increase biotic (pathogens) and abiotic (drought) tolerance of plants.

Hormones can also be added to the core if desired. Procedure:

The granules of fertilizer were put in a coating pan and one monomer with- part of the hormone was added. The coating pan rotated until the granules were covered with one monomer containing part of the hormones, then a second monomer with the rest of the hormones and catalyst were added. The coating pan rotated and the mixture was heated up to 50 °C. When the condensation polymerization ended, and when the granules are not sticky, talcum was added followed by melted wax. The coating pan was rotated continuously. The formulation is then put in bags.

The formulations are summarized in Table 1 :

Table 1 Envelop formulation on fertilizer (KN0₃, MKP)

Example No. Amount Amount Glycols I Ion nones KNO3, g Voranate Extrusion

M580, g

Type Amount, type amount Talc, g Wax, g Fertilizer % Polye¬

8 thylene %

1 (Al ) 100 10 PEG-6U0 10 2-4DP 1 5 5

2. (A12) 100 10 PEG-600 10 2-4DP 0.5 5 5

3. (A2) 100 10 PIΪG-60U 10 2-4 ϋ 1 5 5

4. (A22) 100 10 PEG-60U 10 2-4D 0.5 5 5

5. (Dl) 100 10 PEG-1000 10 2-4DI' 1 5 5

6. (B12) 100 10 I'EG-1000 10 2-4 DP 10.5 5

7. (B2) 100 10 PEG- 1000 10 2-4D 1 5 5

8. (B22) 100 10 PEG- 1000 10 2-4D 0.5 5 5

9. (Cl) 100 5 PEG-6000 15

10. (C2) 100 5 I'EG-6000 15 2-4 D 1 10 5

11. (C22) 100 5 PEG-6000 15 2-4 D 0.5 10 5

12. (Dl) 100 5 l'Eg- 12000 15 2-4 DP 1 10 5

13 (D2) 100 5 PEG-12000 15 2-4D 1 10 5

14. (E03) - - - - - - - - 80 20

15 (El l) - - - - 2-4 DP 1 - - 50 50

16. (E12) - - - - 2-4DP 1 - - 70 30

17. (E42) - - - - 113A 0.5 - - 75 25

18 (E112) - - - - 2-4DP 0.5 - - 50 50

19. (E512) 25g+25g - - - 2-4DP 0.5 - - 50 50

MKP

20. (E532) 25 I A 0.5 50 50

25g MKP

21. (I) 100 5 EDA+DETA O.8-10.7 I I3A 0.1 15 10 +0.2g 11₂0

22. (II) 100 4 EDΛ+DETΛ 1 1 1 2-4D 1 - 10 0.5g 11₂0

Table 1 (cont)

Example No. Amount Amount Glycols Iloimones KNO3, g Voranate Type Amount, type amount Talc, g Wax, g Fertilizer % Polye-

M580, g i. thylene %

23. (Ill) 100 10 EDΛiDEI'Λ 0.8-10.7 PB-zol 0.5 - 5 0.3 g 11₂0

24. (IV) 100 5 EDAfDEIΛ HI MKP 0.1 - 10

25. (V) 100 4 EDA+DETA 111 2-4-DP 0.1 - 10

26. (VI) 100 10 EDA+DEIA HI 2-4-DP 0.5 - 5

27. (VII) 100 10 I- A 1 DEI A 111 2-4-D) PB-zol 0.540.5 - 10

28. (GSK-1) 100 10 EDA+DEIA l-il 2.4D 1 5 5

29. (GSK-2) 100 10 EDAlDETA 1+1 2-4D 1 5 5

30. (GSK-3) 100 10 EDAtDETA HI PB-zol 1 5 5

31. (GSK-5) 100 10 EDAt-DEI^'A HI 2-4 DP 1 5 5

32. (GSK-6) 100 10 EDA+DETA 111 2-4DP+PI3-zol 05 0.5 5 5

33. (GSK-7) 100 10 EDA+DEIA 111 2-4D+PB-zυI 0.5)0.5 5 5

34. (GSK-8) 100 10 EDA+DEIA 1H 2-4DP) PB-zol iIBA 0.5)0.5 + 0.5 5 5

35. (GSK-10) 100 10 EDAt-DEIA HI PB-zol+IBA 0.510.5 5 10

36. (GSK-9) 100 10 EDA+DETA HI PB-zol 0.5 - 10

37. (GSK-11) 100 10 EDA+DETA HI PB-zol ιIBA 2-4D 0.51-0.5)0.5 - 10

38. (GSK-12) 250 25 EDAl ETA 25ι25 PU-zol IIBΛ+2DP 1.25ιl.25ι1.25

39. GSK-13) 250 25 EDA+DETA 2.5+2.5 PB-zol + lBA+2DP 1.25+1.25+1.25 25 0.05 g

40. (GSK-14) 250 30 EDA-t DETA 3+3 IBA-)PB-zol+2DP 1.25 H.25+1.25 - 25 0.05 g

41. (GSK-15) 250 25 EDA+DEI'Λ 2.5)2.5 IBΛi PB-zol 0.6+0.6 - 25

42. (GSK-16) 250 30 EDTΛrEDΛ 3 3 IBΛ PB-ZOD2DP 0.6)0.6)^0.6 - 25

43. (GSK-17) 250 30 DETA 1 EDA 3ι3 IUΛιPB-ZOl^2DP 06+0.6)0.6 - 25

44. (GSK-18) 100 10 EDA+DETA 05)0.5 GΛ₃ 0.5 5 5

45. (GSK-19) 100 10 EDΛi EI^'Λ 1)1 PB-ZOL flllΛ 0.5)0.5 5 10 8g Benlate

46. (GSK-20) 100 10 EDA) DETA HI IBΛil'B-zυl 0.5)0.5 5 5 2g Pυlpane

47. (GSK-21) 100 10 EDA+DE^'IΛ HI IBA+ PB-zol 0.5+0.5 5 5 2g Met pan

48. (GSK-22) 100 10 EDA 1 DETA 111 IBΛ=PB-zol 0.5)0.5 5 5 2g Prochkitaz

Table 1 (cont.)

Example No. Amount Amount Glycols I loimoiiϋs KNO3, g Voranate

M580, g

Type Amount type aiiHHint Talc, g Wax, g reitilizer % Polyethylene %

49. (GSK-23) 100 10 EDΛiDETΛ HI IBΛ+PB-zo 0.510.5 5 5 2g Propionazol

50. (GSK-24) 100 10 EDA 1 DETA 0.5+0.5 5 5 2g Diazinone

51. (GSK-25) 100 10 EDΛi ETΛ 0.510.5 5 5 5g TiGo

52. (GSK-26) 100 10 EDΛiDEI^'Λ 0.510.5 5 5 5g Fe 0₃

53. (GSK-27) 100 10 EDΛ+DE1A 0.5+0.5 5 5 lg Benzoyladenine

54. (GSK-28 100 10 EDA 1 DETA 0.5)0.5 5 5 lg Benlate

55. (GSK-29) 100 10 EDA+DEIA 0.510.5 PB-zi 5 5 -

56. (GSK-30) 100 10 EDA+DEI^'Λ 0.510.5 5 5 2.25 g Meipan

57. (GSK-31) 100 10 EDΛiDETΛ 0.5+0.5 5 5 2g Starch

58. (1) 100 10 EDA 1 DETA 1 ) I 5 5 0.5 g Mg(N0₃)₂

59. (2) 100 10 EDA t DE IΛ 111 5 5 0.5 g Na₂I3 θ7

60. (3) 100 10 EDΛ+DETΛ 1+1 5 5 0.5 g FeSθ4

61. (4) 100 10 EDA) DETA HI 5 5 0.5 g Zn S0₄

62. (5) 100 10 EDA 1 DETA 1+1 5 5 0.5 g Ca (N0₃)₂

63. (6) 100 10 EDΛ+DETΛ HI 5 5 0.5 g M11SO4

100 10 ED+DETΛ HI 5 5 0.5 (Nll4)6MO₇O₂4

Biological methods:

Each cutting was put in a vessel with special earth and with 3 granules, the cuttings were put in green houses. The amount of roots and the length of the roots were measured.

The plants utilized included were Phelargonium: roses, melloloica, olives from different clutivars, eucalyptus of different kinds and many others. The biological tests were carried out with up to 7,000 cuttings for each plant. These tests consisted of various soft cuttings easy-to-root, semi-woody cuttings medium-to- root, difficult-to-root cuttings and grasses.

Select formulations were tested.

The biological results on several kinds of plants are summarized in tables 2-7.

TABLE 2

BIOASSAY BASED ON MUNG-BEAN CUTTINGS TO TEST EFFECT OF ENCAPSULATED FERTILIZERS

Treatment Average No. Average Root Length CM

Roots 6 Days 10 days after treatment

Control (H O) 2.5 0.4 0.9

LBA 21.7 0.2 0.4

GSK-10 39.9 0.6 1.1

GS -30 42.2 0.5 1.0

TABLE 3

EFFECT OF ENCAPSULATED FERTILIZERS GSK10 ON ROOTING OF CUTTINGS OF OLIVE CULTIVARS

Cultivar Percent of Average No. Root Average Root

Rooting Length ( :m)

Control

Manzanillo 26 2.3 7.6

Barnea 49 4.0 5.0

Nabali 31 3.5 6.3

Chimlali 19 3.7 4.5

Maalot 22 1.6 5.9

T-8

(Conventional Treatment)

Manzanillo 48 3.6 4.2

Barnea 73 4.8 3.4

Nabali 52 4.4 5.2

Chimlali 46 5.1 4.0

Maalot 54 3.8 4.7

GSK-10

Manzanillo 52 5.3 8.8

Barnea 89 6.1 9.6

Nabali 61 5.8 7.2

Chimlali 58 5.6 6.6

Maalot 76 4.5 7.9

Table 4

EFFECT OF GSK-10 ON ROOTING OF VARIOUS PLANT SPECIES. THE TRAIL

WAS DONE WITH 7000 CUTTINGS AT "GAT" COMMERCIAL NURSERY

Table 5

EFFECT OF GSK-10 ON DEVELOPMENT OF ROOT SYSTEM OF CUTTINGS OF

EUCALYPTUS

Root svstem development ladder:

+ Roots distributed in less than 25% of the pot medium ++ Roots distributed in about 50% of the pot medium +÷+ Roots distribution in morethan 75% of the pot medium

Treatment

Clone control T-8 GSK-10

Anulata + + ÷ ++++

Gillii + -r +++

Ficifolia - + +++

Kruseana - + + +

Popolnea + + +++

TABLE 6

EFFECT OF ENCAPSULATED FERTILIZERS ON SHOOT DEVELOPMENT OF OLIVE ROOTED PLANTS

Treatment Average ϊ Shoot Elon gation (cm)

30 Days 60 days after treatment

T-8 2.2 4.3

(Conventional treatment)

A_x 1.8 4.1

A₂ 4.0 7.3

TABLE 7

EFFECT OF ENCAPSULATED FERTILIZERS GSK-10 ON VEGETATIVE AND REPRODUCTIVE DEVELOPMENT OF SOLANUM BLUE ROOTED PLANTS

Treatment Transplanting date Average Root Average Number of height CM flowers/plants

Conventional (T-8) March 10 43 9 GSK-10 April 17 87 26

The release rate was determined by the following method, one gram of the granules were placed in a dissolution system. Samples were taken from the vessels and the amount released was determined in the following way: the amount of the fertilizer by conductometeric method and the amount of the hormone by HPLC.

Very promising results concerning the rate of root formation, length of roots, survival of plants and ease of high mass plant production were clearly observed.

The formulations were found to be most effective in: accelerating root formation, increasing rooting percentage, improving the quality of root system, and stimulation of young plant (vegetative and reproductive) development in comparison to untreated control and IBA talc powder (the common substance used at present for rooting in all nurseries).

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative examples and that the present invention may be embodied in other specific forms without departing from the essential attributes thereof, and it is therefore desired that the present embodiments and examples be considered in all respects as illustrative and not restrictive, reference being made to the appended claims, rather than to the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims

What is claimed is:

1. A controlled-release encapsulated fertilizer comprising a core containing at least one fertilizer and a polymeric envelope containing at least one hormone encapsulating said fertilizer.

2. A controlled-release encapsulated fertilizer according to claim 1 , wherein said envelope contains at least one hormone selected from the group consisting of Auxin; indole alkyl acid; indole acetic acid(IAA); indole propionic acid(IPA); indole butyric acid(IBA); 2,4 dichlorophenoxy acetic acid; 2,4 chlorophenoxy propionic acid; 2,4 dichloro phenoxyacetic acid propyl ester; and, Naphthalene acetic acid.

3. A controlled-release encapsulated fertilizer according to claim 1 , wherein said polymeric envelope is formed by a polymer selected from the group consisting of polyurethane; polyurea; and, polyolefins.

4. A controlled-release encapsulated fertilizer according to claim 1 , further comprising a triazole incorporated therein.

5. A controlled-release encapsulated fertilizer according to claim 4, wherein said triazole is paclobutrazole.

6. A controlled-released encapsulated fertilizer according to claim 1 , further comprising a cytokinine incorporated therein.

7. A controlled-released encapsulated fertilizer according to claim 6, wherein said cytokinine is benzoyladenine.

8. A controlled-released encapsulated fertilizer according to claim according to claim 1 , furhter comprising a carbohydrate incorporated therein.

9. A controlled-released encapsulated fertilizer according to claim 8, wherein said carbohydrate is selected from the group consisting of glucose, sucrose and starch.

10 A controlled-released encapsulated fertilizer according to claim 1 , further comprising a fungicide incorporated therein.

11. A controlled-released encapsulated fertilizer according to claim 10, wherein said fungicide is selected from the group consisting of Benelate, folpane, merpan and propionazal.

12. A controlled-released encapsulated fertilizer according to claim 1 , furhter comprising an insecticide incorporated therein.

13. A controlled-released encapsulated fertilizer according to claim 12, wherein said insecticide is diazinone or nephorex.

14. A process for encapsulating a fertilizer comprising: a) coating a fertilizer with a mixture of a first monomer and a hormone; b) adding a mixture of a second monomer and an additional hormone; and, c) heating said mixtures to induce the polymerization of said first and second monomers to form a polymeric envelope incorporating said hormone and encapsulating said fertilizer.

15. A process for encapsulating a fertilizer according to claim 14, wherein said envelope contains at least one hormone selected from the group consisting of Auxin; indole alkyl acid; indole acetic acid(IAA); indole propionic acid(IPA); indole butyric acid(IBA); 2,4 dichlorophenoxy acetic acid; 2,4 dichloro phenoxyacetic acid propyl ester; and, Naphthalene acetic acid.

16. A process for encapsulating a fertilizer according to claim 14, wherein said polymeric envelope is formed by a polymer selected from the group consisting of polyurethane; polyurea; and, polyolefins.

17. A process for encapsulating a fertilizer according to claim 14, wherein said envelope contains at least one hormone selected from the group consisting of Auxin; (indole alkyl acid; indole acetic acid(IAA); indole propionic acid(IPA); indole butyric acid(IBA); 2,4 dichlorophenoxy acetic acid; 2,4 dichloro phenoxyacetic acid propyl ester; and, Naphthalene acetic acid), and further optionally comprising at least one further component selected from the group consisting of a growth retardant, a cytokinine, a carbohydrate, a fungicide and an insecticide.